Methods for producing crystalline microporous solids with IWV topology and compositions derived from the same

ABSTRACT

This disclosure relates to new crystalline microporous solids (including silicate- and aluminosilicate-based solids), the compositions comprising 8 and 10 membered inorganic rings, particularly those having IWV topologies having a range of Si:Al ratios, methods of preparing these and known crystalline microporous solids using certain quaternized imidazolium cation templates.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalPatent Application Nos. 61/930,326, filed Jan. 22, 2014; 61/969,963,filed Mar. 25, 2014; 62/054,247, filed Sep. 23, 2014; 62/013,167, filedJun. 17, 2014; and 62/077,719, filed Nov. 10, 2014, the contents of eachof which are incorporated by reference in their entirety herein.

TECHNICAL FIELD

This disclosure relates to new crystalline microporous solids (includingsilicate- and aluminosilicate-, and other metal-silicate-based solids),the various compositions comprising 8, 10, 12, and 14-membered inorganicrings, particularly those having RTH, HEU, CIT-7, and IWV topologieshaving a wide range of Si:Al ratios. This disclosure also providesmethods of preparing these and known crystalline microporous solidsusing certain quaternized imidazolium cation organic structure directingagents, and intermediates used in these methods.

BACKGROUND

It is estimated that over 90% of chemical processes use a catalyst, with80% being a heterogeneous catalyst, with a global demand of $15 to $20billion per year. Microporous materials (pores less than 2 nm) are animportant type of heterogeneous catalyst as they offer shape and sizeselective environments for catalysis to occur. Additionally, they oftenexhibit robust hydrothermal stability which allows them to be used underdemanding process conditions, such as fluid catalytic cracking.Synthetic aluminosilicate zeolites are produced on a scale 1.7-2 millionmetric tons per year, and their use as catalysts comprises 27% of theworld market for zeolites. As the cost of the catalyst is estimated tobe only 0.1% of the cost of the final product, the demand to innovate inthis area remains high. There currently exist over 200 known microporousmaterial frameworks, but of these less than 20 have been commercializedand the market is dominated by only five major frameworks. In manyapplications, there is only a single structure and composition toachieve optimal performance, motivating much of the research directed atcreating new materials.

In recent years there has been considerable interest in 8-MR systems forcatalysis and separations. Some of the most promising catalyticapplications are the methanol to olefins (MTO) conversion and deNOx.Other 8-MR materials of interest are LEV, CHA and AFX. It has been foundthat the cage size and connectivity are critical in determining theproduct distribution for these reactions in 8-MR systems. As RTHpossesses a unique connectivity as well as cage size it exhibits uniquecatalytic performance, which has been shown for MTO using thealuminosilicate material. The RTH topology has 8-MR openings and a2-dimensional (“2-D”) channel system with pore sizes of 4.1×3.8 Å and5.6×2.5 Å, leading to larger cages. See also C. Baerlocher, L. B.Mccusker, Database of Zeolite Structures, approved by the StructureCommission of the International Zeolite Association, and available at<http://www.izastructure.org/databases/>, (2014).

The molecular sieve (zeolite) with the framework topology of RTH wasfirst described in 1995. It was produced as a borosilicate (RUB-13)using the relatively simple organic structure directing agent (“OSDA”)1,2,2,6,6-pentamethylpiperidinium. Although the borosilicate requires aless exotic OSDA, the small pores of the material prevent thereplacement of boron with aluminum. However, in order to produce analuminosilicate material with the necessary acid strength for the MTOreaction, a more complicated OSDA was required. The next RTH microporousmaterial was produced as an aluminosilicate (SSZ-50) using2-ethyl-2,5,7,7-tetramethyl-2-azabicyclo[4.1.1]octan-2-ium as thestructure directing agent.

But this OSDA requires an elaborate multi-step synthesis adding to thecost and complexity of the preparation, so as to be unlikely thismaterial would be used in commercial production. Some progress has beenmade to synthesize a OSDA-free version of RTH using seed crystals, butmaterials so-produced have a very limited compositional range.Additionally, the high Si/Al ratios (Si/Al=41 and 108) may be less thanoptimal for a catalyst. For all of these reasons an alternative SDA toproduce RTH is desired so that it can be tested for applications.

Microporous solids having 2-dimensional channels and 8-MR and 8-/10-MRframeworks are finding increasing utility as catalysts, ion exchange,and adsorption systems. The heulandite (HEU) framework is anothertopology having a 2-dimensional channel system, and relatively largepore sizes. In the [001] directing there are 10-membered rings (MRs) aswell as 8-MRs. Additionally, there is another set of 8-MRs along with[100] direction.

Heulandite materials are divided into two distinct classes based onSi/Al ratio. Those with Si/Al of less than 4 are known as heulandite andthose with Si/Al greater than 4 are known as clinoptilolite, orsilica-rich heulandite. The key difference in these materials is thatthose with Si/Al of less than 4 are not thermally stable to calcinationabove 350° C. A method to produce a high-silica heulandite was firstreported by removing aluminum from natural clinoptilolite to make amaterial with Si/Al=5.5, known as LZ-219. Later, methods were developedto produce synthetic heulandite across a range of Si/Al=2.5-6 usingvarious sources of silica and alumina and a wide range of inorganiccations (Li, Na, K, Rb, Ca) under hydrothermal synthesis (without theuse of OSDAs) or acid leaching conditions. These materials have beenconsidered for applications such as gas cleaning and separations, ionexchange, isomerization of 1-butene and xylene, methanol dehydration andacetylene hydration. In any of these applications, the ability to tailorthe framework composition is important for material properties such asexchange capacity, hydrothermal stability and pore accessibility.

Crystalline microporous solids of the IWV framework were first preparedas the ITQ-27 framework using the phosphorus-containingstructure-directing agent, dimethyldiphenylphosphonium. Its structurecomprises seven unique T-sites forming a framework with straight 12-MRchannels that are connected by 14-MR openings between them. Since accessfrom one 14-MR opening to the next is through the 12-MR channel, thestructure is best described as a two-dimensional, 12-MR framework. OtherITQ structures are known to have larger (e.g., 12-/14-MR) and smallerring openings, making these materials useful for hydrocarbon processing.

Much of the discovery of new microporous material frameworks andcompositions in recent years has resulted from the use of organicstructure directing agents (OSDAs), which are normally alkylammoniumcations. While OSDAs have led to many new materials, their costcontributes a significant portion of the material cost, which oftencannot be recovered as they are normally removed from the material usingcombustion. In some systems it is possible to partially replace highcost OSDAs with cheaper organics, such as with SSZ-13 where it has beenshown that over 80% of the expensive trimethyl-N-1-adamantammoniumhydroxide OSDA can be replaced with the much cheaper benzyl trimethylammonium hydroxide. Another way is to find methods to synthesize thematerials in the absence of OSDAs, but this can often lead to limitedproduct compositions and still does not eliminate processing steps suchas ion exchange and calcination. Therefore, an attractive route to lowerOSDA costs is to find new, simpler OSDAs to synthesize desiredmaterials.

For at least these reasons, interest is currently high in developing newmolecular sieves having 2-dimensional channel systems with 8-MR and8-/10-MR openings and 12-MR openings.

SUMMARY

The present invention is directed to several new crystalline microporoussolids, having 2-dimensional channel systems with 8-MR, 8-/10-MR, and12-MR channels, and methods of preparing the same. One set comprisescrystalline material having an RTH topology generally (includingSSZ-50), and especially aluminosilicate compositions having low Si:Alratios, and methods for preparing these types of materials across a widerange of Si/Al including low Si/Al ratios. A second set, describedherein as CIT-7, is a new crystal form, and includes a broad range ofcompositions having 2-dimensional channels with 8-MR and 10-MR. A thirdset of materials comprises solids having HEU topology, having 2dimensional channels and 8-MR and 8-/10-MR openings, especiallyaluminosilicate materials having high Si:Al ratios. High silica HEU,denoted CIT-8 (California Institute of Technology number 8) can beprepared via topotactic condensation of a layered aluminosilicatematerial containing an organic structure directing agent. This layeredmaterial is denoted CIT-8P. CIT-8 can also be prepared by directsynthesis in hydroxide media using an imidazolium organic structuredirecting agent (OSDA). A fourth material, which has the IWV frameworkstructure contains a 2-dimensional system of 12-MR channels, which leadto internal 14-MR rings and is prepared at previously unknowncompositions.

Also described are the processes and intermediates used in making suchcompositions. Such compositions and methods include the use of organicstructure defining agents (OSDAs) including quaternized imidazoliumcations (“quats”) and linked pairs of quaternary imidazolium cations(“diquats”). These materials have shown good activity for themethanol-to-olefins reaction (MTO) and have also been proposed as amaterial for catalytic NO_(X) reduction. Industrially, imidazoles areproduced using the Radziszewski reaction or by dehydrogenation ofimidazolines and are available in high purity. The quaternaryimidazolium cations of the present invention can then be prepared bystandard alkylation methods.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, processes, devices, and systemsdisclosed. In addition, the drawings are not necessarily drawn to scale.In the drawings:

FIG. 1 shows representative powder X-ray diffraction (XRD) patterns ofone of the RTH compositions produced by the present methods: as-made(lower) and calcined (upper) aluminosilicate RTH zeolites forcomposition prepared using 1 SiO₂:0.5 Al:0.5 ROH:0.5 HF:14 H₂O, whereROH is pentamethylimidazolium hydroxide.

FIG. 2 shows representative powder X-ray diffraction (XRD) patterns forcalcined aluminosilicate RTH prepared in hydroxide media (sample H4), asdescribed in Example 4.

FIG. 3 and FIG. 4A-C show Scanning Electron Micrographs (SEMs) formaterials prepared in Example 1.3. FIG. 4A shows SEM of calcined RTHprepared in fluoride media (sample F4). FIG. 4B shows SEM of calcinedRTH synthesized in hydroxide media with sodium (sample H4). FIG. 4Cshows SEM of calcined RTH synthesized in hydroxide media without sodium(sample H5).

FIG. 5 shows a ¹³C NMR spectra of pentamethylimidazolium in D₂O withmethanol standard (lower), ¹³C CP-MAS NMR of as-made RTH prepared inhydroxide media (middle, sample H4) and ¹³C CP-MAS NMR of as-made RTHprepared in fluoride media (upper, sample F4).

FIG. 6 shows ²⁷Al MAS NMR spectra of low silica RTH synthesized inhydroxide media (lower, sample H1) and prepared in fluoride media(upper, sample F2). The single resonance is at 54 ppm.

FIG. 7 show an argon isotherm for aluminosilicate RTH prepared inhydroxide media with product Si/Al=14 (sample H4).

FIG. 8A-G shows MTO reactivity data for various compositions describedherein. FIG. 8A shows data for SSZ-13 with Si/Al=19; FIG. 8B shows datafor SAPO-34; FIG. 8C shows data for fresh Si/Al=17 RTH (sample H6); FIG.8D shows data for Si/Al=17 RTH (sample H6; regenerated one time); FIG.8E shows data for Si/Al=17 RTH (sample H6; regenerated two times); FIG.8F shows data for Si/Al=29 RTH (sample H8); FIG. 8G shows data forSi/Al=59 (sample H10), showing methanol conversion (open diamonds) to C₂olefins (solid squares), C₃ olefins (solid triangles), C₄ olefins (soliddiamonds), total C₁-C₄ alkanes (open circles), and C₅'s+C₆'s (solidcircles).

FIGS. 9A and 9B shows representative powder X-ray diffraction (XRD)patterns for calcined pure silicate RTH prepared in fluoride. Thepatterns are for the as-made material (FIG. 9A, lower), material treatedwith ozone at 150° C. to remove the organic (FIG. 9A, middle) andcalcined material (FIG. 9A, upper and FIG. 9B).

FIG. 10 shows representative powder X-ray diffraction (XRD) pattern forcalcined pure silica CIT-7 material (made with2-ethyl-1,3-dimethylimidazolium cation) containing an ITW impurity,marked with *. See Example 8.1.

FIG. 11 shows representative powder X-ray diffraction (XRD) pattern forcalcined pure-silica CIT-7 produced in fluoride media using3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium) cation.See Example 8.1.

FIG. 12 shows representative powder X-ray diffraction (XRD) pattern forcalcined aluminosilicate CIT-7 produced in fluoride media with the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium) cationand gel Si/Al=50, as described in Example 8.

FIGS. 13A and 13B show representative powder X-ray diffraction (XRD)patterns for as-made CIT-7 (FIG. 13A) and calcined CIT-7 (FIG. 13B)produced in hydroxide media with the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium) cationand gel Si/Al=15, as described in Example 8.1.

FIG. 14 shows the 3-dimensional ED tomography data used to solve thestructure of CIT-7.

FIG. 15 shows the Rietveld refinement fit (Rwp=0.077; Rexp=0.068;RF=0.055). Upper traces: synchrotron data; Middle traces: calculateddata; Lower traces: difference. Upper inset is magnified 6 times.

FIG. 16 shows a view along the 10-membered ring channel system of CIT-7.

FIG. 17 shows a view along the 8-membered ring channel system of CIT-7.

FIG. 18 shows the secondary building units found in CIT-7.

FIG. 19 shows an assembly of the CIT-7 framework from secondary buildingunits. The mtw and the new [4⁴5²] (cse) composite building unitsassembled to form a repeating building unit. The connection of thebuilding units forms a chain. The arrangement of the chain forms a layerwith distorted 8-rings. Connection of the layers forms 10-ring channelsthat are intersected with the 8-ring channels.

FIG. 20 show the isosurface contours of CIT-7

FIG. 21 shows the ¹³C CP-MAS NMR spectrum of as-made CIT-7 (upper)showing the occluded3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium) cationalong with peak assignments and comparison to the liquid ¹³C NMRspectrum (lower).

FIG. 22 shows an Argon isotherm of CIT-7, micropore volume determined tobe 0.19 cm³/g (t-plot method).

FIG. 23 shows an ²⁹Si MAS NMR spectrum of calcined pure silicate CIT-7(upper) and the deconvolution of ²⁹Si MAS NMR spectrum of calcined puresilicate CIT-7 (lower).

FIG. 24 shows an ²⁷Al MAS NMR spectrum of aluminosilicate CIT-7. Upperis fluoride mediated synthesis with gel Si/Al=15 and lower is hydroxidemediated synthesis with gel Si/Al=5. The sample made in hydroxide mediais 95% tetrahedral aluminum and the sample made in fluoride media is 88%tetrahedral aluminum.

FIG. 25 shows a UV-VIS spectrum of titanosilicate CIT-7.

FIG. 26A and FIG. 26B show representative powder X-ray diffraction (XRD)patterns for calcined IWV, as described in Example 8.1. FIG. 26A shows apattern for calcined IWV produced in hydroxide media at Si/Al=15. FIG.26B shows a pattern for as-made (lower) and calcined (upper) IWVproduced in fluoride media at gel Si/Al=50

FIG. 27 shows a representative powder X-ray diffraction (XRD) patternfor as-made CIT-8P, as described in Example 9.1.

FIG. 28 shows a representative powder X-ray diffraction (XRD) patternfor calcined CIT-8, as described in Example 9.1.

FIG. 29 shows representative powder X-ray diffraction (XRD) pattern forcalcined HEU made in hydroxide media, as described in Example 9.1.

FIG. 30A show a ²⁷Al MAS NMR spectrum for calcined HEU produced inhydroxide media. The single resonance in this spectrum is consistentwith tetrahedral aluminum, that is aluminum in the framework. FIG. 30Bshow a ²⁷Al MAS NMR spectrum for calcined HEU produced in fluoridemedia. The majority of the aluminum in this sample is tetrahedral butthere is a small amount of octahedral aluminum (0 ppm).

FIG. 31 shows representative powder X-ray diffraction (XRD) patterns foras-made pure-silica STW (lower) and calcined pure-silica STW (upper), asdescribed in Example 9.1.

FIG. 32 shows representative powder X-ray diffraction (XRD) patterns foras-made STW+ layered (lower) and calcined STW (upper), as described inExample 9.1

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to crystalline microporous solids ofHEU, RTH, CIT-7, and IWV topologies, and processes and intermediatesused in making such crystalline materials. Such compositions and methodsinclude the use of organic structure defining agents includingquaternized imidazolium cations and linked pair of quaternaryimidazolium cations.

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, processes, conditions or parameters described or shown herein,and that the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe invention herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this specification, claims, anddrawings, it is recognized that the descriptions refer to compositionsand processes of making and using said compositions. That is, where thedisclosure describes or claims a feature or embodiment associated with acomposition or a method of making or using a composition, it isappreciated that such a description or claim is intended to extend thesefeatures or embodiment to embodiments in each of these contexts (i.e.,compositions, methods of making, and methods of using).

TERMS

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method or process steps; (ii) “consisting of” excludes anyelement, step, or ingredient not specified in the claim; and (iii)“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention. Embodimentsdescribed in terms of the phrase “comprising” (or its equivalents), alsoprovide, as embodiments, those which are independently described interms of “consisting of” and “consisting essentially of.” For thoseembodiments provided in terms of “consisting essentially of,” the basicand novel characteristic(s) of a process is the ability to provide amicroporous material having the designated topologies, and of a productor intermediate, one having the designated topology.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are described herein.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The terms “halo” and “halogen” are used in the conventional sense torefer to a chloro, bromo, fluoro, or iodo substituent.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of solvents orother impurities; additional embodiments include those where thecompound is substantially the only solute in a solvent or solventfraction, such a analytically separated in a liquid or gaschromatography phase.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesembodiments where the circumstance occurs and instances where it doesnot. For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present. Similarly, the phrase “optionally isolated” means thatthe target material may or may not be separated from other materialsused or generated in the method, and, thus, the description includesseparate embodiments where the target molecule or other material isseparated and where the target material is not separated, such thatsubsequence steps are conducted on isolated or in situ generatedproduct.

The terms “separating” or “separated” carries their ordinary meaning aswould be understood by the skilled artisan, insofar as it connotesseparating or isolating the product material from other startingmaterials or co-products or side-products (impurities) associated withthe reaction conditions yielding the material. As such, it infers thatthe skilled artisan at least recognizes the existence of the product andtakes specific action to separate or isolate it. Absolute purity is notrequired, though preferred, as the material may contain minor amounts ofimpurities and the separated or isolated material may contain residualsolvent or be dissolved within a solvent used in the reaction orsubsequent purification of the material.

As used herein, the term “crystalline microporous solids” or“crystalline microporous silicate or aluminosilicate solids,” sometimesreferred to as “molecular sieves,” are crystalline structures havingvery regular pore structures of molecular dimensions, i.e., under 2 nm.The term “molecular sieve” refers to the ability of the material toselectively sort molecules based primarily on a size exclusion process.The maximum size of the species that can enter the pores of acrystalline microporous solid is controlled by the dimensions of thechannels. These are conventionally defined by the ring size of theaperture, where, for example, the term “8-MR” or “8-membered ring”refers to a closed loop that is typically built from eight tetrahedrallycoordinated silicon (or aluminum) atoms and 8 oxygen atoms. In thepresent case, the structures described comprise 8- or 8- and 10-memberedrings or 12-membered rings (designated 8-MR, 8-/10-MR, and 12-MR,respectively). These rings are not necessarily symmetrical, due to avariety of effects including strain induced by the bonding between unitsthat are needed to produce the overall structure, or coordination ofsome of the oxygen atoms of the rings to cations within the structure.The term “silicate” refers to any composition including silica. It is ageneral term encompassing, for example, pure-silica, aluminosilicate,borosilicate, or titanosilicate structures. The term “zeolite” refers toan aluminosilicate composition that is a member of this family.

The present invention is directed to several new crystalline microporoussolids, having 2-dimensional channel systems with 8-MR, 8-/10-MRopenings and 12-MR openings, and methods of preparing the same. One setcomprises crystalline material having an RTH topology generally(including SSZ-50), and especially aluminosilicate compositions havinglow Si:Al ratios, and methods for preparing these types of materials. Asecond set, described herein as CIT-7, is a new crystal form, andincludes a broad range of compositions having 2 dimensional channels and8-/10-MR openings. A third set of materials comprises solids having HEUtopology, having 2-dimensional channels and 8-/10-MR openings,especially aluminosilicate materials having high Si:Al ratios. A fourthset of material comprises solids having IWV topologies, having2-dimensional channels and 12-MR framework, especially thosecompositions having high Si:Al ratios. Additional embodiments aredirected to methods of making these new compositions. These new methodsmay also be used to prepare compositions having known Si:Al ratios.

In some embodiments, the crystalline microporous solids may becharacterized by the dimensions and directions of the rings (Table 1).

TABLE 1 Representative dimensions of the compositions described herein(from IZA) 8-MR [001]^(a) 10-MR [001]^(a) 8-MR [100]^(a) 8-MR [010]12-MR [001]^(a) 12-MR [011]^(a) CIT-7 5.1 × 6.2 Å 2.9 × 5.5 Å HEU 3.6 ×4.6 Å 3.1 × 7.5 Å 2.8 × 4.7 Å (CIT-8) RTH 2.5 × 5.6 Å 3.8 × 4.1 Å IWV6.2 × 6.9 Å 6.2 × 6.9 Å ^(a)[001], [100], [010], and [011] refer tocrystallographic directions. Such directions are provided for guidanceonly, and may vary slightly in some embodiments. It is understood thatthese ring directions are for ideal materials. In real materials, smalldeviations occur.

The inventive processes may be described, at least in part, in terms ofhydrothermally treating a composition comprising a silicate source,aluminosilicate source, or metallosilicate source in the presence of anOrganic Structure Directing Agent (“OSDA”), described herein andselected depending on the nature of the desired product, underconditions sufficient to form the desired crystalline product, andoptionally recovering and further processing the crystalline products.These as-synthesized crystalline materials may contain occluded OSDAwithin their pore structures, which can be removed by thermal oroxidative treatments. One of the many advantages of the OSDAs of thepresent invention over phosphorus-containing OSDAs is that they avoidthe inclusion of P atoms or oxides on calcining which inevitably occuron use of the phosphorus-containing OSDAs. Similarly, the compositionsassociated with these processes are also considered within the scope ofthe invention.

Some embodiments include processes (and compositions) for preparingcrystalline microporous solids, each process comprising hydrothermallytreating a composition comprising:

(a) (i) at least one source of a silicon oxide, germanium oxide, orcombination thereof; and optionally

-   -   (ii) at least one source of aluminum oxide, boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zirconium oxide, or combination or        mixture thereof; and

(b) a linked pair of quaternary imidazolium cations of a structure:

under conditions effective to crystallize a crystalline microporoussolid;

wherein t is 3, 4, 5, or 6, preferably 4 or 5; and

R is independently methyl or ethyl, preferably methyl or mainly methyl,and n is independently 1, 2, or 3; said linked pair of quaternaryimidazolium cations having associated fluoride or hydroxide ions,preferably substantially free of other halide counterions, i.e.,bromide, chloride, or iodide. As used herein, the term “linked pair ofquaternary imidazolium cations” is intended to connote that twoquaternary imidazolium cations are linked by the carbon linker, and notthat the two quaternized cations are necessarily identical, though thisis preferred.

Subsets of this embodiment include those where (a) comprises only atleast one source of a silicon oxide, germanium oxide, or combinationthereof, preferably only at least one source of a silicon oxide. Suchmethods are useful for producing crystalline silicate microporous solidshaving an RTH, or CIT-7 topology. Additional subsets of this embodimentinclude those where (a) comprises only at least one source of a siliconoxide and at least one source of aluminum or titanium oxide. Suchmethods are useful for producing crystalline microporous solids,especially aluminosilicates or titanosilicates having CIT-7, HEU, RTH orIWV topologies.

In preferred embodiments, the composition being hydrothermally treatedcomprises only at least one source of silicon oxide or at least one formof silicon oxide and at least one source of aluminum oxides, for thepreparation of crystalline microporous silicate and aluminosilicatesolids, respectively. In some specific cases, sources of titanium oxidemay be substituted or used in conjunction with the sources of aluminumoxide.

As described in the Examples below, depending on specific reactionconditions, particularly temperature and water:Si ratio, the productcrystalline microporous silicate solid may independently have an RTH orHEU (e.g., designated CIT-8 or CIT-8P) or IWV or a topology designatedas CIT-7.

As used throughout, the counterions of the organic structure directingagents are fluoride or hydroxide, and substantially free of other halidecounterions, i.e., bromide, chloride, or iodide. In this context, theterm “substantially free” refers to a condition where no bromide,chloride, or iodide are added to the composition or process, and infact, reasonable efforts are taken to remove these from the compositionor process, e.g., by ion exchange methods. It does not require absoluteabsence of these anions, as for example, as may result from incidentalresidual bromide, chloride, or iodide contained within the inorganicmaterials.

In other embodiments, it may be desirable to hydrothermally treat atleast one source of a silicon oxide, germanium oxide, or combinationthereof under analogous conditions.

The dication designation shown in Formula (I) may also be characterizedby the resonance structures shown here, reflecting the nature of thecationic charge distribution over the imidazolium cations.

In certain preferred embodiments, the linked pair of quaternaryimidazolium cations has a structure:

where t is 3, 4, 5, or 6; and the associated ions are preferablyhydroxide. When t=3, 4, or 5, in some cases, compositions of the CIT-8Ptype morphology can be prepared. When t=3, 4, or 5, in some cases, theformation of CIT-7 type morphology appears to be favored, whereas whent=5, in some cases, the formation of the RTH topology is favored. IWVcan be formed when t=4, 5, or 6 (see, e.g., Tables 9, 9B, 14, and 15 andExample 7.2).

In some embodiments, the a linked pair of quaternary imidazolium cationsmay be described not only with respect to ethyl and methyl groups, butalso in terms of a C/N+ ratio, where the C represents the number ofcarbon atoms and N+ represents the number of quaternized nitrogen atomsassociated with each imidazolium cation. In these embodiments, the C/N+ratio for each imidazolium can be independently in the range of from t6:1 to 10:1, preferably from 6:1, from 7:1, or from 8:1 to 9:1, morepreferably 8:1. For the purpose of counting carbon atoms, the linkingcarbon chain is considered to provide a single carbon atom to eachimidazolium cation. For example, in the embodiment where t is 5, and thelinked pair of quaternary imidazolium cations has associated hydroxideions, the linked pair of quaternary imidazolium cations may berepresented by the structure:

each imidazolium cation would have eight associated carbon atoms (3 ringcarbons, 4 methyl carbons, and one linking carbon) and one chargedquaternary nitrogen atom, for a C/N+ ratio of 8:1. Since, by thisdefinition, the linking carbon chain provides only a single carbon toeach imidazolium cation, this ratio would be independent of the value oft. (Note that other definitions sometimes used in the art provide for anaccounting of all of the carbons in the linking chain. In thisconvention, the values for C/N+ ratio are correspondingly higher toaccount for all of the linking carbon atoms. For example, by thisconvention, the example above would have nineteen associated carbonatoms (6 ring carbons, 8 methyl carbons, and five linking carbons) andtwo charged quaternary nitrogen atoms, for a C/N+ ratio of 19:2 or9.5:1).

Other embodiments relate to processes for the preparation of crystallinemicroporous solids, each process comprising hydrothermally treating acomposition comprising:

-   -   (a) (i) at least one source of silicon oxide and        -   (ii) at least one source of aluminum oxide, boron oxide,            gallium oxide, hafnium oxide, iron oxide, tin oxide,            titanium oxide, indium oxide, vanadium oxide, zirconium            oxide, or combination or mixture thereof in the presence of            an organic complex comprising    -   (b) an imidazolium cation comprising methyl and ethyl groups and        having a C/N+ ratio in a range of from 6:1 to 10:1, preferably        from 6:1, from 7:1, or from 8:1 to about 9:1, or 8:1, such that        the imidazolium has, for example,        -   (i) 3, 4, or 5 methyl groups or        -   (ii) 2, 3, or 4 methyl groups and one ethyl group and    -   (c) an associated hydroxide or fluoride anion, preferably        hydroxide and preferably substantially free of other halide        counterions, i.e., bromide, chloride, or iodide;        under conditions effective to crystallize an RTH-, HEU, CIT-7-,        or IWV-type crystalline microporous solid.

In some preferred embodiments, the processes are used to preparecrystalline aluminosilicate solids. Such embodiments include thosecomprising hydrothermally treating a composition comprising:

(a) (i) at least one source of a silicon oxide, germanium oxide, orcombination thereof;

-   -   (ii) at least one source of aluminum oxide; and optionally    -   (iii) at least one source of boron oxide, gallium oxide, hafnium        oxide, iron oxide, tin oxide, titanium oxide, indium oxide,        vanadium oxide, zirconium oxide, or combination or mixture        thereof; and

(b) an imidazolium cation comprising methyl and ethyl groups and havinga C/N+ ratio in a range of from 6:1 to 10:1, preferably from 6:1, from7:1, or 8:1 to 9:1, more preferably 8:1, such that the imidazolium, forexample, has (i) 3, 4, or 5 methyl groups or (ii) 2, 3, or 4 methylgroups and one ethyl group, and (iii) a hydroxide or fluoride anion,preferably substantially free of other halide counterions, i.e.,bromide, chloride, or iodide;

under the conditions effective to crystallize an RTH-, HEU-, CIT-7, orIWV-type crystalline microporous solid, preferably an aluminosilicatesolid (described herein; see Examples 3-9 for exemplary conditions).

Again, the separate formation of each of the RTH-, HEU, CIT-7, orIWV-type crystalline microporous solid can be directed by the separatechoice of temperature, water:Si ratios, and other parameters, some ofwhich are described in the Examples as specific embodiments. Forexample, the RTH topology can be obtained using HF or hydroxide-mediatedconditions, at temperatures ranging from about 100° C. to about 200° C.,preferably from about 150° C. to about 180° C., or more preferably fromabout 160° C. to about 175° C. and a water:Si ratio ranging from about2:1 to about 20:1, preferably from about 4:1 to about 10:1 in fluoridemediated syntheses or from about 2:1 to about 40:1, preferably fromabout 15:1 to about 20:1 in hydroxide mediated syntheses. Non-limiting,exemplary conditions are shown, e.g., in Examples 3, 5 and 7.

The CIT-7-type topology can be obtained using HF or hydroxide-mediatedconditions, at temperatures ranging from about 150° C. to about 180° C.,or preferably from about 160° C. to about 175° C. and at lower water:Siratios (e.g., from about 2:1 to about 5:1), with silicates in HFmediated syntheses, or with aluminosilicates (Si:Al ratios from about15:1 to about 250:1, preferably about 20:1) in HF- or hydroxide-mediatedsyntheses, using OSDAs comprising monoquat imidazolium cations orpreferably those having linked pairs of quaternized imidazolium cations,where the linking chain length is 3-5 carbons, preferably about 4carbons. Non-limiting, exemplary conditions are shown, e.g., in Examples3 and 8.

The HEU topology can be obtained using HF or hydroxide-mediatedconditions, at temperatures ranging from about 100° C. to about 200° C.,preferably from about 150° C. to about 180° C., or more preferably fromabout 160° C. to about 175° C. and at lower water:Si ratios (e.g., fromabout 4:1 to about 7:1) and Si:Al ratios (e.g., from about 5:1 to about50:1, preferably from about 5:1 to about 20:1), using OSDAs havinglinked pairs of quaternized imidazolium cations, where the linking chainlength is 3-5 carbons. Non-limiting, exemplary conditions are shown,e.g., in Examples 3 and 9.

While the pure silicate-containing crystalline microporous solids andthe HEU and CIT-7 topologies appear to require, or at least favor, theuse of the linked pair of quaternary imidazolium cations, othercrystalline materials appear to favor the use of mono-quaternaryimidazolium cations having the parameters described above. Exemplaryimidazolium cations include those aromatic structures described by aresonance form that is:

Typical sources of silicon oxide for the reaction mixtures includealkoxides, hydroxides, or oxides of silicon, or combination thereof.Exemplary compounds also include silicates (including sodium silicate),silica hydrogel, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicates, and silica hydroxides.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum alkoxides, aluminumoxide coated on silica sol, hydrated alumina gels such as Al(OH)₃ and asodium aluminate. Sources of aluminum oxide may also comprises analkoxide, hydroxide, or oxide of aluminum, or combination thereof.Additionally, the sources of alumina may also comprise other ligands aswell, for example acetylacetonate, carboxylates, and oxalates; suchcompounds are well known as useful in hydrothermal or sol-gel syntheses.

Sources of boron oxide, gallium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, and/or zirconiumoxide can be added in forms corresponding to their aluminum and siliconcounterparts.

In other embodiments, a source inorganic reagent may also provide asource of aluminum. In some cases, the source inorganic also provides asource of silicate. The source zeolite in its dealuminated form may alsobe used as a source of silicate, with additional silicon added using,for example, the conventional sources listed above. Use of a sourcezeolite reagent as a source of alumina for the present process is morecompletely described in U.S. Pat. No. 4,503,024, the disclosure of whichis incorporated herein by reference.

In those cases where the source of silicon or aluminum is an alkoxide,their respective empirical formulae are preferably Si(OR)₄ and Al(OR)₃,where R is an alkyl group of 1-6 carbon atoms, including methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, hexyl Some of these compounds, especially Al(OR)₃, formcomplicated bridging structures in solution, even before hydrolysis. Insome embodiments, the silicon alkoxide is tetraethyl orthosilicate(TEOS) and the aluminum alkoxide is Al(i-OPr)₃.

In the processes directed to preparing the aluminosilicate zeolites,some embodiments provide that the ratio of Si:Al in the composition isin a range of from about 5:1 to about 250:1. Additional embodimentsinclude those where the ratio is in a range bounded at the lower end bya value of about 5:1, 10:1, 15:1, 20:1, or 25:1 and bounded at the upperend by a value of about 250:1, 100:1, 50:1, 30:1, 25:1, 20:1, 15:1, orabout 10:1. In those embodiments where some of the Al are substituted byB, Ga, Hf, Fe, Sn, Ti, In, V, or Zr, these ratios refer to the ratio ofSi:(Al+B, Ga, Hf, Fe, Sn, Ti, In, V, and/or Zr). In some cases, theselead to crystalline compositions having Si:Al ratios which are lowerthan the forming compositions (see, e.g., Table 5). In other cases, thecrystalline compositions may have Si:Al ratios which are higher than theforming compositions (see, e.g., Table 15).

The compositions of these processes may also include mineralizing mediaincluding aqueous HF or aqueous hydroxide. Where the media compriseaqueous hydroxide, the source of the hydroxide may be an alkali metalhydroxide and/or an alkaline earth metal hydroxide, such as thehydroxide of sodium, potassium, lithium, cesium, rubidium, barium,calcium, and magnesium, is used in the reaction mixture. The OSDA may beused to provide hydroxide ion, thereby reducing or eliminating thealkali metal hydroxide quantity required. The alkali metal cation oralkaline earth cation may be part of the as-synthesized crystallineoxide material, in order to balance valence electron charges therein.

In some embodiments, the ratio of imidazolium cation:Si is in a range offrom about 0.05:1 to about 1:1. In the embodiments where the OSDA is alinked pair of quaternary imidazolium cations, each imidazolium moietyis considered individually. Certain embodiments provide preferredratios, depending on the nature of the mineralizing system; i.e.,whether it is hydroxide mediated or fluoride mediated. In the fluoridemediated systems, certain preferred embodiments include those where therange of the imidazolium cation:Si ratio is in a range of from about0.2:1 to about 1:1, more preferably about 0.5:1. In hydroxide mediatedsystems, the preferred imidazolium cation:Si is typically in a range offrom about 0.05:1 to about 1:1, preferably about 0.2:1.

In other embodiments, the ratio of water:Si is in a range of from about2:1 to about 20:1, preferably in a range of from about 4:1 to about10:1. Additional embodiments include those where the range is bounded atthe lower end by a value of about 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1,9:1, 10:1, 12:1, 14:1, 16:1, 18:1, or 20:1 and bounded at the upper endby a value of about 20:1, 18:1, 16:1, 14:1, 12:1, or about 10:1. As withsome of the other parameters, the preferred water:Si ratio may depend onthe inorganic system, whether it is hydroxide mediated or fluoridemediated. In the fluoride mediated systems, a preferred water:Si rangeis from about 2:1 to 20:1 and most preferably 4:1 to 10:1. In hydroxidemediated system, a preferred water: Si range is from about 2:1 to 40:1and most preferably about 15-20:1.

In processing the crystalline microporous solids, the reaction mixtureis maintained at an elevated temperature until the crystals of thedesired product form are formed. The hydrothermal crystallization isusually conducted under autogenous pressure, at a temperature between100° C. to about 200° C., preferably about 140° C. to about 180° C. orfrom about 160° C. to about 180° C., for a time effective forcrystallizing the desired crystalline microporous solid. Thecrystallization period is typically greater than 1 day and preferablyfrom about 1 day to about 40 days, or from about 3 days to about 20days. Preferably, the zeolite is prepared using mild stirring oragitation.

During the hydrothermal crystallization step, the crystallinemicroporous solids can be allowed to nucleate spontaneously from thereaction mixture. The use of product crystals as seed material can beadvantageous in decreasing the time necessary for completecrystallization to occur. In addition, seeding can lead to an increasedpurity of the product obtained by promoting the nucleation and/orformation of the desired crystalline microporous solid over anyundesired phases. When used as seeds, such seed crystals are added in anamount between 0.1 and 5% or between 0.1 and 10% of the weight ofsilicate-source used in the reaction mixture.

Once the crystals have formed, the solid product can be separated fromthe reaction mixture by standard mechanical separation techniques suchas filtration or centrifugation. The crystals can be water-washed andthen dried, e.g., at 90° C. to 150° C. for from 8 to 24 hours, to obtainthe as-synthesized crystalline microporous solids. The drying step canbe performed at atmospheric pressure or under vacuum.

In various embodiments, the processes described herein produce or arecapable of producing compositionally “clean” crystalline microporousmaterials. That is, in various embodiments, the crystalline microporousmaterials described herein are at least 75%, 80%, 85%, 90%, 95%, or 98%by weight of the nominal topology. In some embodiments, the crystallinemicroporous materials exhibit XRD patterns where other crystallinetopologies are undetectable.

Similarly, in various embodiments the as-formed, calcined, or dopedmicroporous materials that are free from phosphorus atoms or oxides.

The hydrothermal processes provide as-synthesized crystalline materialshaving the desired topology which contain the imidazolium OSDAs used toprepare the materials occluded in the pore structures, and thesecompositions are considered within the scope of the present invention.

The crystalline microporous solids can be used as-synthesized, butpreferably are thermally treated (calcined), in part to remove theoccluded organic OSDAs. For example, in certain embodiments, theisolated as-synthesized crystalline intermediate are treated underoxidative (e.g., air or oxygen) or inert atmosphere at at least onetemperature in a range of from about 350° C. to about 850° C. or about1000° C. When a strongly oxidizing atmosphere is uses (e.g., ozone), thetemperature is generally lower, for example, in a range from about 25°C. to about 200° C. In some embodiments, the as-synthesizedintermediates are calcined first under an inert atmosphere to pyrolyzethe organic occlusions, then calcined in air (optionally including addedO₂ or ozone) to remove the deposited carbon. In other embodiments, theas-synthesized zeolites are calcined directly under oxidizingconditions. Representative ramp rates are provided in the Examples. Notethat the calcining or pyrolysis reactions result in the formation ofcrystalline microporous materials that are free from P atoms or oxides,a distinguishing feature over materials made from some other methods.

It is also often desirable to remove any alkali metal cation by ionexchange and replace it with hydrogen, ammonium, or any desired metalion. The zeolite can be leached with chelating agents, e.g., EDTA ordilute acid solutions, to increase the silica to alumina mole ratio. Thecrystalline microporous solid can also be steamed; steaming helpsstabilize the crystalline lattice to attack from acids. Alternatively,or additionally, the calcined materials may be treated with aqueousammonium salts (e.g., NH₄NO₃) to remove any residual inorganic cationsin the pores of the crystalline solid.

The crystalline microporous solids can be used in intimate combinationwith hydrogenating components, such as tungsten, vanadium molybdenum,rhenium, nickel cobalt, chromium, manganese, or a noble metal, such aspalladium or platinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the crystalline microporous solid byreplacing some of the cations in the crystalline microporous solid withmetal cations via standard ion exchange techniques. (see, for example,U.S. Pat. No. 3,140,249 issued Jul. 7, 1964 to Plank et al.; U.S. Pat.No. 3,140,251 issued Jul. 7, 1964 to Plank et al.; and U.S. Pat. No.3,140,253 issued Jul. 7, 1964 to Plank et al.). Typical replacingcations can include metal cations, e.g., rare earth, Group 1, Group 2and Group 8 metals, as well as their mixtures. Cations of metals such asrare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe areparticularly preferred.

Following contact with the salt solution of the desired replacingcation, the crystalline microporous solid is typically washed with waterand dried at temperatures ranging from 65° C. to about 200° C. Afterwashing, the crystalline microporous solid can be calcined in air orinert gas at temperatures ranging from about 25° C. to about 200° C. orfrom about 200° C. to about 850° C. or about 1000° C., as describedabove and depending on the nature of the calcining atmosphere, forperiods of time ranging from 1 to 48 hours or more, to produce acatalytically active product especially useful in hydrocarbon conversionprocesses. Regardless of the cations present in the synthesized form ofthe crystalline microporous solid, the spatial arrangement of the atomswhich form the basic crystal lattice of the crystalline solid remainsessentially unchanged.

The crystalline microporous solids may also be treated under conditionsso as to incorporate at least one type of transition metal or transitionmetal oxide catalyst into the pore structure, for example by vapor orchemical deposition or precipitation. As used herein, the term“transition metal” refers to any element in the d-block of the periodictable, which includes groups 3 to 12 on the periodic table. In actualpractice, the f-block lanthanide and actinide series are also consideredtransition metals and are called “inner transition metals. Scandium,yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum,tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel,palladium, platinum, copper, silver, gold, or mixtures thereof arepreferred.

The as-synthesized or calcined crystalline microporous solids can beformed into a wide variety of physical shapes. Generally speaking, thezeolite can be in the form of a powder, a granule, or a molded product,such as extrudate. In cases where the catalyst is molded, such as byextrusion with an organic binder, these crystalline solids can beextruded before drying, or, dried or partially dried and then extruded.The crystalline microporous solids can be composited with othermaterials resistant to the temperatures and other conditions employed inorganic conversion processes. Such matrix materials include active andinactive materials and synthetic or naturally occurring crystallinesolids, including zeolites, as well as inorganic materials such asclays, silica and metal oxides.

To this point, the embodiments have been described mainly in terms ofprocesses to prepare the crystalline microporous solids, but thecompositions used in these processes are also considered within thescope of the present invention(s). For the sake of completeness, some ofthese are repeated here, but this partial listing should not beinterpreted as abandoning those embodiments not specifically listed.

Certain embodiments include those compositions, especially useful forpreparing crystalline microporous silicate solids, comprising:

(a) at least one source of a silicon oxide (optionally includinggermanium oxide, or combination thereof);

(b) a linked pair of quaternary imidazolium cations of a structure:

wherein t is 3, 4, 5, or 6, preferably 4 or 5; and

R is independently methyl or ethyl, and n is independently 1, 2, or 3;

said linked pair of quaternary imidazolium cations having associatedfluoride or hydroxide ions, and as more broadly described as above; and

(c) optionally at least one crystal of a compositionally consistentcrystalline HEU, RTH, CIT-7, or IWV solid. In this regard, thecompositions preferably, but not necessarily, contain crystals of anyone of the compositionally consistent crystalline HEU, RTH, or CIT-7solid. In some of these embodiments, a portion of the linked pair ofquaternary imidazolium cations is occluded in the pores of the crystals.

Certain additional embodiments include those compositions, especiallyuseful for preparing other crystalline microporous solids, saidcompositions comprising:

(a) at least one source of a silicon oxide (germanium oxide, orcombination thereof);

(b) at least one source of aluminum oxide, boron oxide, gallium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, zirconium oxide, or combination or mixture thereof; and

(c) an imidazolium cation comprising methyl and ethyl groups and havinga C/N+ ratio in a range of from 6:1 to 10:1, preferably from 6:1, from7:1, or from 8:1 to 9:1 or 8:1, such that the imidazolium has, forexample,

-   -   (i) 3, 4, or 5 methyl groups or    -   (ii) 2, 3, or 4 methyl groups and one ethyl group and

(c) a hydroxide or fluoride anion, preferably substantially free ofother halide counterions, i.e., bromide, chloride, or iodide; and

(d) optionally a compositionally consistent crystalline HEU, RTH, CIT-7,or IWV solid. Again, in this regard, a preferred embodiment is acomposition useful for creating aluminosilicate products—i.e., where atleast one source of source of aluminum oxide is present. Also, andagain, the compositions preferably, but not necessarily, containcrystals of any one of the compositionally consistent crystalline HEU,RTH, CIT-7, or IWV solid. In some of these embodiments, a portion of theimidazolium cation is occluded in the pores of the crystals.

Additional embodiments include those described above, as well asembodiments where the composition does independently contain acrystalline HEU, RTH, CIT-7, or IWV composition, and particularly acompositionally consistent crystalline HEU, RTH, CIT-7, or IWVcomposition. As used herein, the term “compositionally consistentcrystalline HEU, RTH, CIT-7, or IWV composition” describes a crystallinecomposition that has the same topology of the named framework, andpreferably is a silicate version of that topology or the crystallinecomposition contains the same types of oxides as do the sources ofoxides, albeit not necessarily in the same atomic or molecularproportions—e.g., derived from added seed crystals, hydrothermallyformed crystals, or both. Here, the term “substantially free” refers tothe absence of added materials having different topologies than thepresent RTH, HEU, or CIT-7 crystals, again which may be present eitheras added seed crystals or as formed during hydrothermal treatment of thecomposition.

The imidazolium cations used in the compositions, especially useful forpreparing these crystalline materials, may be described by a resonanceform that is:

The sources of silicon oxide, aluminum oxides, boron oxide, galliumoxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indiumoxide, vanadium oxide, and/or zirconium oxide used in these compositionsare as described above in terms of the processes.

Similarly, the specific chemistries associated with the HF and hydroxidemediated processes (including ratios of imidazolium cation to Si, waterto Si, and Si to Al) and described above are also considered within thedescription of the corresponding compositions.

In certain separate embodiments, the compositions are solutions or gels,as understood by those of ordinary skill in this art.

Also considered within the scope of the present invention(s) are thosecrystalline compositions comprising a crystalline microporous solid,prepared by any of the processes described herein, eitheras-synthesized, calcined, or otherwise modified. Some of theseembodiments include those crystalline silicate compositions having anRTH structure, an HEU structure, a CIT-7 structure, or an IWV structureand having pores at least some of which are occluded with a linked pairof quaternary imidazolium cations of a structure:

including those OSDAs as more fully described above, and thosecrystalline compositions having pores, at least some of which areoccluded with an organic complex comprising (a) an imidazolium cationcomprising methyl and ethyl groups and having a C/N+ ratio in a range offrom 6:1 to 10:1, preferably from 6:1, from 7:1, or from 8:1 to 9:1,more preferably 8:1.

As described below, specific embodiments include those crystallinecompositions having an RTH structure, an HEU structure, a CIT-7structure, or an IWV structure where the occluded linked pair ofimidazolium cations (“diquat”) or mono-quaternized imidazolium cationsaccording (“monoquats”) can be described by a resonance form that is:

The specific nature of the occluded linked pair of imidazolium cations(“diquat”) or mono-quaternized imidazolium cations according(“monoquats”) in each case reflects that OSDA used in the preparation ofthe specific crystalline microporous material.

The crystalline compositions containing the occluded linked pair ofquaternary imidazolium cations or quaternized imidazolium cation includethose compositions where the ratio of Si:Al is in a range of from about5:1 to about ∞:1 (i.e., pure silicate). Additional independentembodiments include those crystalline compositions with the occludedOSDA where the ratio of Si:Al is in a range from about 4:1 to 5:1, fromabout 5:1 to about 7.3:1, from about 7.3:1 to about 10:1, from about10:1 to about 12.3:1, from about 12.3:1 to about 15:1, from about 15:1to about 17.3:1, from about 17.3:1 to about 20:1, from about 20:1 toabout 25:1, from about 25:1 to about 30:1, from about 30:1 to about50:1, from about 50:1 to about 75:1, from about 75:1 to about 100:1,from about 100:1, from about 100:1 to about 250:1, from about 250:1 toabout ∞:1, or a combination of two or more of these ranges. Note that aSi:Al ratio of infinity (∞) corresponds to a silicate compositionsubstantially free of Al.

Still further embodiments include those calcined, doped, or otherwisemodified crystalline compositions having RTH, HEU, CIT-7, or IWVstructures prepared by these inventive methods, and absent the occludedlinked pair of quaternary imidazolium cations or imidazolium cations,that exhibit Si:Al ratios over one or more of these ranges.

Additional embodiments include those crystalline microporous solidshaving an RTH structure, absent the occluded linked pair of quaternaryimidazolium cations or imidazolium cations (i.e., where these organicmaterials have been removed) comprising (a) silicon oxide and (b)aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconiumoxide, or combination thereof, wherein the molar ratio of (a) to (b) isin a range of from about 5 to about 20, from about 5 to about 15, fromabout 5 to about 10, or from about 10 to about 15. In certain of theseembodiments, the frameworks of these crystalline aluminosilicatezeolites contain oxides of silicon and at least aluminum. In certain ofthese embodiments, the solids exhibit an XRD diffraction pattern thesame as or consistent with that shown in FIG. 1, FIG. 2, or FIG. 9A/B,reflective of the pore sizes comparable to or the same as thosedescribed in Table 1. In other embodiments, the crystalline RTH solidexhibits a single peak in the ²⁷Al MAS spectrum, in some cases having achemical shift 54 ppm downfield of a peak corresponding to aqueousAl(NO₃)₃ as shown in FIG. 6. In other embodiments, these microporoussolids contain the doped metals or transition metals or oxides describedherein. Additional characteristics of these materials may be found inthe Examples.

Still further embodiments include those crystalline microporous solidshaving an HEU structure, absent the occluded linked pair of quaternaryimidazolium cations or imidazolium cations (i.e., where these organicmaterials have been removed) comprising (a) silicon oxide and (b)aluminum oxide and optionally boron oxide, gallium oxide, hafnium oxide,iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide,zirconium oxide, or combination thereof, wherein the molar ratio of (a)to (b) is in a range of from about 5 to about 7.3, from 7.3 to about 10,from about 10 to about 12.3, from about 12.3 to about 15, from about 15to about 17.3, from about 17.3 to about 20, or a combination of two ormore of these ranges. In certain of these embodiments, the frameworks ofthese crystalline aluminosilicate zeolites contain only alumina andsilica. In certain embodiments, these crystalline microporous silicateor aluminosilicate solids having an HEU structure were prepared byeither topotactic condensation from a layered precursor material,denoted CIT-8P, or by direct synthesis, as described herein.

In certain other of these embodiments, the crystalline microporous solidhaving an HEU structure exhibit an XRD diffraction pattern the same asor consistent with that shown in FIG. 27, FIG. 28, or FIG. 29,reflective of the pore sizes comparable to or the same as thosedescribed in Table 1. In other embodiments, these crystallinemicroporous solids contain the doped metals or transition metals oroxides described herein. In some embodiments, the crystallinemicroporous solid having an HEU structure exhibits a ²⁷Al MAS NMRspectrum that is the same as or consistent with the spectra of thatshown in FIG. 30A or FIG. 30B. Additional characteristics of thesematerials may be found in the Examples.

Additional embodiments include those crystalline microporous solidshaving a topology as described as CIT-7, absent the occluded linked pairof quaternary imidazolium cations or imidazolium cations (i.e., wherethese organic materials have been removed) comprising either a puresilicate structure, or an structure comprising (a) silicon oxide and (b)aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconiumoxide, or combination thereof, preferably aluminosilicates. Theframework structure has been determined from a combination of rotationelectron diffraction and synchrotron X-ray powder diffraction data, andmay be defined in the following terms. The structure has 10crystallographically unique tetrahedral atoms (T-atoms) in the unitcell, and can be described as an ordered arrangement of the [4²5⁴6²] mtwbuilding unit and a previously unreported [4⁴5²] building unit. Theframework contains a 2-dimensional pore system that is bounded by 10T-atom rings (10-ring, 5.1 Å*6.2 Å opening) that are connected with oval8-rings (2.9 Å*5.5 Å opening) through medium-sized cavities (7.9 Å) atthe channel intersections.

In certain of these embodiments, the frameworks of these crystallinemicroporous CIT-7 solids contain oxides of silicon and at leastaluminum. In other embodiments, these crystalline zeolites containoxides of silicon and titanium. In certain of these embodiments, thesolids exhibit an XRD diffraction pattern the same as or consistent withthat shown in FIG. 11, FIG. 12, or FIG. 13A/B, reflective of the poresizes comparable to or the same as those described in Table 1. In otherembodiments, the crystalline silica CIT-7 solid exhibits a plurality ofpeak in the ²⁹Si MAS spectrum, in some cases having chemical shifts ofabout 115.59, about 115.19, 111.2, 109.58, 109.27, 108.81, and about106.735 ppm downfield of a peak corresponding to tetramethylsilane asshown in FIG. 23. Aluminosilicate versions of CIT-7 may exhibit ²⁷Al MASspectrum corresponding to FIG. 24. Other additional characteristics ofthese materials may be found in the Examples. In other embodiments, thecrystalline silicate CIT-7 solid can be characterized by thecrystallographic parameters substantially as described in Table 11. Instill other embodiments, these crystalline microporous CIT-7 solidscontain the doped metals or transition metals or oxides describedherein.

Additional embodiments include those crystalline microporous solidshaving an IWV topology, absent the occluded linked pair of quaternaryimidazolium cations or imidazolium cation (i.e., where these organicmaterials have been removed) comprising either a pure silicatestructure, or an structure comprising (a) silicon oxide and (b) aluminumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination thereof, preferably aluminosilicates. Some embodimentsprovide that these structures exhibit a characteristic XRD diffractionpattern as shown in FIG. 26A or FIG. 26B. In some other embodiments,these IWV frameworks are pure silicates or aluminosilicates, having aSi:Al ratio of about 7.3:1, or in a range of from about 4:1 to about5:1, from about 5:1 to about 10:1, from about 10:1 to about 15:1, fromabout 15:1 to about 20:1, from about 20:1 to about 25:1, from about 25:1to about 30:1, from about 30:1 to about 50:1, from about 50:1 to about100:1, from about 100:1 to about 250:1, from about 250:1 to infinity, orany combination of these ranges. Note that a Si:Al ratio of infinity (∞)corresponds to a silicate composition substantially free of Al.

The various crystalline structures described herein are convenientlydescribed in terms of their characteristic XRD diffraction patterns.Certain embodiments include those structures exhibiting any one of theXRD patterns shown in any one of the Figures of this specification.Tables 2A and 2B provide tabulations of major peaks within eachspectrum, and separate embodiments include those structures having atleast the five major peaks of each spectrum, and optionally additionalpeaks, preferably in order of decreasing relative heights (intensities).

TABLE 2A Representative XRD data for structures described in thisspecification Calcined pure silica RTH Calcined SiAl-RTH CalcinedSi-CIT-7 Calcined topotactic HEU (CIT-8) Relative Relative RelativeRelative 2-θ (deg) Height 2-θ(deg) Height 2-θ(deg) Height 2-θ (deg)Height 8.56 100.0 8.56 94.7 7.43 100.0 10.02 100 9.03 89.0 9.06 100.08.26 100.0 11.28 32.9 10.09 28.7 10.14 53.8 9.62 13.6 13.12 18.5 10.1841.0 17.70 10.1 10.08 18.0 13.42 8.4 12.42 2.9 18.76 28.0 10.48 19.917.38 12.5 17.71 7.5 19.52 15.3 14.83 9.5 22.51 20.6 18.79 18.4 19.839.2 18.42 7.8 22.76 26.6 19.61 11.3 23.13 11.4 22.96 7.6 26.44 7.8 25.097.6 25.00 17.0 23.55 6.7 28.29 7.0 30.75 2.9 25.49 13.2 25.02 8.5 30.359.5

TABLE 2B Representative XRD data for structures described in thisspecification As-made layered HEU Hydroxide Calcined IWV (CIT-8P) HEU(Si/Al = 15) Calcined STW 2-θ(deg) Relative Height 2-θ(deg) RelativeHeight 2-θ(deg) Relative Height 2-θ(deg) Relative Height 7.17 100.0 9.6418.2 6.02 13.7 9.05 42.6 11.41 11.9 9.95 100.0 6.40 100.0 10.44 100.014.15 26.6 11.22 49.9 7.09 16.8 12.40 29.7 16.13 13.2 13.09 27.3 7.9012.8 14.73 27.6 18.12 19.4 17.35 28.8 7.99 61.0 17.35 32.0 19.84 32.922.46 40.8 9.49 9.3 22.76 31.2 21.93 10.1 22.72 46.8 12.85 9.7 22.9334.7 22.71 9.8 26.28 20.6 19.04 14.9 23.52 24.0 24.40 22.4 30.25 24.421.07 10.7 25.82 24.9 25.19 22.1 32.05 15.2 26.71 12.2 26.01 31.7

As described herein, the variation in the scattering angle (two theta)measurements, due to instrument error and to differences betweenindividual samples, is estimated at ±0.15 degrees. The X-ray diffractionpatterns shown in this application are considered representative of“as-synthesized” or “as-made” and calcined crystalline structures. Minorvariations in the diffraction pattern can result from variations in the,e.g., silica-to-alumina mole ratio of the particular sample due tochanges in lattice constants. In addition, sufficiently small crystalswill affect the shape and intensity of peaks, leading to significantpeak broadening. Calcination can also result in changes in theintensities of the peaks as compared to patterns of the “as-made”material, as well as minor shifts in the diffraction pattern. Thecrystalline solids produced by exchanging the metal or other cationspresent in the solids with various other cations (NH₄ ⁺ and thencalcining to produce H⁺) yields essentially the same diffractionpattern, although again, there may be minor shifts in the interplanarspacing and variations in the relative intensities of the peaks.Notwithstanding these minor perturbations, the basic crystal latticeremains unchanged by these treatments. Accordingly, the skilled artisanwould expect that a description that structures having XRD patterns withpeaks within such small variances shown in Tables 2A and 2B would stillbe considered within the scope of this invention.

The calcined crystalline microporous solids, calcined or doped ortreated with the catalysts described herein may also be used ascatalysts for a variety of chemical reactions, including hydrocrackinghydrocarbons, dewaxing hydrocarbon feedstocks, isomerizing hydrocarbonsincluding olefins, producing higher molecular weight hydrocarbons fromlower molecular weight hydrocarbons, converting lower alcohols and otheroxygenated hydrocarbons to produce liquid products including olefins,reducing the content of oxides of nitrogen contained in a gas stream inthe presence of oxygen, and separating nitrogen from anitrogen-containing gas mixture. In each case, the processes includecontacting the respective feedstock with the catalyst under conditionssufficient to affect the transformation. Such transformations are knownto those of ordinary skill in the art.

In various embodiments, the crystalline microporous solids mediate orcatalyze an array of chemical transformation. As follows, each of thecrystalline solid materials will have utility in at least each of thefollowing applications, though it is believed that those having 8-MRstructures (i.e., RTH, HEU, and CIT-7) will be especially useful inconverting lower alcohols and other oxygenated hydrocarbons to produceliquid products including olefins, reducing the content of oxides ofnitrogen contained in a gas stream in the presence of oxygen, andseparating nitrogen from a nitrogen-containing gas mixture. Thosecompositions having 10-MR (i.e., HEU, CIT-7) or 12-MR (IWV) will beuseful in hydrocarbon processing.

Some embodiments provide processes for converting hydrocarbons, eachprocess comprising contacting a hydrocarbonaceous feed at hydrocarbonconverting conditions with a catalyst comprising a crystallinemicroporous solid of this invention. The crystalline material may bepredominantly in the hydrogen form, partially acidic or substantiallyfree of acidity, depending on the process.

Other embodiments provide hydrocracking processes, each processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form.

Still other embodiments provide processes for dewaxing hydrocarbonfeedstocks, each process comprising contacting a hydrocarbon feedstockunder dewaxing conditions with a catalyst comprising a crystallinemicroporous solid of this invention, preferably predominantly in thehydrogen form.

Yet other embodiments provide processes for improving the viscosityindex of a dewaxed product of waxy hydrocarbon feeds, each processcomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising a crystalline microporoussolid of this invention, preferably predominantly in the hydrogen form.

Additional embodiments include those process for producing a C20+ lubeoil from a C20+ olefin feed, each process comprising isomerizing saidolefin feed under isomerization conditions over a catalyst comprising atleast one transition metal catalyst and a crystalline microporous solidof this invention. The crystalline microporous solid may bepredominantly in the hydrogen form.

Also included in the present invention are processes for isomerizationdewaxing a raffinate, each process comprising contacting said raffinatein the presence of added hydrogen with a catalyst comprising at leastone transition metal and a crystalline microporous solid of thisinvention. The raffinate may be bright stock, and the zeolite may bepredominantly in the hydrogen form.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content, each process comprising contacting ahydrocarbonaceous feedstock which comprises normal and slightly branchedhydrocarbons having a boiling range above about 40° C. and less thanabout 200° C., under aromatic conversion conditions with a catalystcomprising a crystalline microporous solid of this invention madesubstantially free of acidity by neutralizing said zeolite with a basicmetal. Also provided in this invention is such a process wherein thecrystalline microporous solid contains a transition metal component.

Also provided by the present invention are catalytic cracking processes,each process comprising contacting a hydrocarbon feedstock in a reactionzone under catalytic cracking conditions in the absence of addedhydrogen with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form. Alsoincluded in this invention is such a catalytic cracking process whereinthe catalyst additionally comprises a large pore crystalline crackingcomponent.

This invention further provides isomerization processes for isomerizingC4 to C7 hydrocarbons, each process comprising contacting a feed havingnormal and slightly branched C4 to C hydrocarbons under isomerizingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form. Thecrystalline microporous solid may be impregnated with at least onetransition metal, preferably platinum. The catalyst may be calcined in asteam/air mixture at an elevated temperature after impregnation of thetransition metal.

Also provided by the present invention are processes for alkylating anaromatic hydrocarbon, each process comprising contacting underalkylation conditions at least a molar excess of an aromatic hydrocarbonwith a C2 to C20 olefin under at least partial liquid phase conditionsand in the presence of a catalyst comprising a crystalline microporoussolid of this invention, preferably predominantly in the hydrogen form.The olefin may be a C2 to C4 olefin, and the aromatic hydrocarbon andolefin may be present in a molar ratio of about 4:1 to about 20:1,respectively. The aromatic hydrocarbon may be selected from the groupconsisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof.

Further provided in accordance with this invention are processes fortransalkylating an aromatic hydrocarbon, each of which process comprisescontacting under transalkylating conditions an aromatic hydrocarbon witha polyalkyl aromatic hydrocarbon under at least partial liquid phaseconditions and in the presence of a catalyst comprising a crystallinemicroporous solid of this invention, preferably predominantly in thehydrogen form. The aromatic hydrocarbon and the polyalkyl aromatichydrocarbon may be present in a molar ratio of from about 1:1 to about25:1, respectively. The aromatic hydrocarbon may be selected from thegroup consisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention are processes to convert paraffins toaromatics, each of which process comprises contacting paraffins underconditions which cause paraffins to convert to aromatics with a catalystcomprising a crystalline microporous solid of this invention, saidcatalyst comprising gallium, zinc, or a compound of gallium or zinc.

In accordance with this invention there is also provided processes forisomerizing olefins, each process comprising contacting said olefinunder conditions which cause isomerization of the olefin with a catalystcomprising a crystalline microporous solid of this invention.

Further provided in accordance with this invention are processes forisomerizing an isomerization feed, each process comprising an aromaticC8 stream of xylene isomers or mixtures of xylene isomers andethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta-and para-xylenes is obtained, said process comprising contacting saidfeed under isomerization conditions with a catalyst comprising thezeolite of this invention.

The present invention further provides processes for oligomerizingolefins, each process comprising contacting an olefin feed underoligomerization conditions with a catalyst comprising a crystallinemicroporous solid of this invention.

This invention also provides processes for converting lower alcohols andother oxygenated hydrocarbons, each process comprising contacting saidlower alcohol (for example, methanol, ethanol, or propanol) or otheroxygenated hydrocarbon with a catalyst comprising a crystallinemicroporous solid of this invention under conditions to produce liquidproducts. Compositions having the RTH topology are expected to beespecially useful in this regard (see, e.g., Example 6).

Also provided by the present invention are processes for reducing oxidesof nitrogen contained in a gas stream in the presence of oxygen whereineach process comprises contacting the gas stream with a crystallinemicroporous solid of this invention. The a crystalline microporous solidmay contain a metal or metal ions (such as cobalt, copper or mixturesthereof) capable of catalyzing the reduction of the oxides of nitrogen,and may be conducted in the presence of a stoichiometric excess ofoxygen. In a preferred embodiment, the gas stream is the exhaust streamof an internal combustion engine.

Additional transformations considered within the scope of the presentinvention mediated by the crystalline materials of the presentinvention, but at least for those crystalline microporous solids of HEU,CIT-7, and IWV topologies, are those described in Table 13.

Specific conditions for each of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961, which isincorporated by reference herein in its entirety for all purposes.

Depending upon the type of reaction which is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. As used herein, “predominantly in thehydrogen form” means that, after calcination, at least 80% of the cationsites are occupied by hydrogen ions and/or rare earth ions.

The following listing of embodiments is intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1

A process comprising hydrothermally treating a composition comprising:

(a) (i) at least one source of a silicon oxide, germanium oxide, orcombination thereof; and optionally

-   -   (ii) at least one source of aluminum oxide, boron oxide, gallium        oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,        indium oxide, vanadium oxide, zirconium oxide, or combination or        mixture thereof; and

(b) a linked pair of quaternary imidazolium cations of a structure:

under conditions effective to crystallize a crystalline microporoussolid;

wherein t is 3, 4, 5, or 6, preferably 4 or 5; and

R is independently methyl or ethyl, preferably methyl, and n isindependently 1, 2, or 3; said linked pair of quaternary imidazoliumcations having associated fluoride or hydroxide ions, preferablysubstantially free of other halide counterions, i.e., bromide, chloride,or iodide. Subsets of this embodiment include those where (a) comprisesonly at least one source of a silicon oxide, germanium oxide, orcombination thereof, preferably only at least one source of a siliconoxide. Such methods are useful for producing crystalline silicatemicroporous solids having an RTH, HEU, CIT-7, or IWV topology.Additional subsets of this Embodiment include those where (a) comprisesonly at least one source of a silicon oxide and at least one source ofaluminum oxide. Such methods are useful for producing at leastcrystalline aluminosilicate microporous solids having a CIT-7 or IWVtopology.

Embodiment 2

The process of Embodiment 1, wherein the composition beinghydrothermally treated comprises only (i) at least one source of siliconoxide or (ii) at least one form of silicon oxide and at least one sourceof aluminum oxide, for the preparation of crystalline microporoussilicate and aluminosilicate solids, respectively.

Embodiment 3

The process of Embodiment 1 or 2, wherein the linked pair of quaternaryimidazolium cations has a structure:

where t is 3, 4, or 5.

Embodiment 4

The process of any one of Embodiment 1 to 3, wherein the linked pair ofquaternary imidazolium cations has a structure:

said linked pair of quaternary imidazolium cations, preferably havingassociated hydroxide ions.

Embodiment 5

A process comprising hydrothermally treating a composition comprising:

-   -   (a) (i) at least one source of silicon oxide and optionally        -   (ii) at least one source of aluminum oxide, boron oxide,            gallium oxide, hafnium oxide, iron oxide, tin oxide,            titanium oxide, indium oxide, vanadium oxide, zirconium            oxide, or combination or mixture thereof;    -   in the presence of an organic complex comprising    -   (b) an imidazolium cation comprising methyl and ethyl groups and        having a C/N+ ratio in a range of from about 6:1 to 10:1,        preferably from 6:1, from 7:1, or from 8:1 to 9:1, more        preferably 8:1, such that the imidazolium has, for example,        -   (i) 3, 4, or 5 methyl groups or        -   (ii) 2, 3, or 4 methyl groups and one ethyl group and    -   (c) a hydroxide or fluoride anion, preferably substantially free        of other halide counterions, i.e., bromide, chloride, or iodide;    -   under conditions effective to crystallize a microporous solid.        Processes for preparing silicates and aluminosilicates are        considered within the scope of preferred embodiments. The        crystalline microporous silicate or aluminosilicate solid may be        one of an RTH, HEU, CIT-7 or IWV topology.

Embodiment 6

The process of Embodiment 5, comprising hydrothermally treating acomposition comprising

(a) (i) at least one source of a silicon oxide, germanium oxide, orcombination thereof;

-   -   (ii) at least one source of aluminum oxide; and optionally    -   (iii) at least one source of boron oxide, gallium oxide, hafnium        oxide, iron oxide, tin oxide, titanium oxide, indium oxide,        vanadium oxide, zirconium oxide, or combination or mixture        thereof; and

(b) an imidazolium cation having (i) 3, 4, or 5 methyl groups or (ii) 2,3, or 4 methyl groups and one ethyl group, and (iii) a hydroxide orfluoride anion, preferably substantially free of other halidecounterions, i.e., bromide, chloride, or iodide;

under conditions effective to crystallize a microporous aluminosilicatesolid. The crystalline microporous aluminosilicate solid may be one ofan RTH, HEU, CIT-7, or IWV topology.

Embodiment 7

The process of Embodiment 5 or 6, wherein the imidazolium cation isdescribed by a resonance form that is:

Embodiment 8

The process of any one of Embodiments 1 to 7, wherein the source ofsilicon oxide comprises an alkoxide, hydroxide, or oxide of silicon, orcombination thereof. Exemplary compounds also include silicates, silicahydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkylorthosilicates, and silica hydroxides.

Embodiment 9

The process of any one of Embodiments 2 to 8, wherein the source ofaluminum oxide comprises an alkoxide, hydroxide, or oxide of aluminum,or combination thereof. Additionally, the sources of alumina may alsoinclude other ligands as well, for example acetylacetonate,carboxylates, and oxalates; such compounds are well known as useful inhydrothermal or sol-gel syntheses.

Embodiment 10

The process of any one of Embodiments 2 to 9, wherein the source ofboron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination or mixture thereof comprises an alkoxide, hydroxide, oxide,or combination thereof of the corresponding metal.

Embodiment 11

The process of any one of claims 1 or 3 to 10, wherein the crystallinemicroporous solid independently exhibits an RTH, HEU, CIT-7, or IWVtopology.

Embodiment 12

The process of any one of Embodiments 1 to 11, wherein the at least onesource of silicon oxide comprise a silicon alkoxide, a silica, a sodiumsilicate, or a combination thereof.

Embodiment 13

The process of any one of Embodiments 2 to 12, wherein the at least onesource of aluminum is an aluminum alkoxide, an aluminate (e.g., oxide,hydroxide, or mixed oxide/hydroxide), a sodium aluminate an aluminumsiloxide, or a combination thereof.

Embodiment 14

The process of Embodiment 12, wherein the silicon alkoxide is of theformula Si(OR)₄, where R is an alkyl group of 1-6 carbon atoms.

Embodiment 15

The process of Embodiment 13, wherein the aluminum alkoxide is of theformula Al(OR)₃, where R is an alkyl group of 1-6 carbon atoms.

Embodiment 16

The process of any one of Embodiments 2 to 15, wherein the ratio ofSi:Al in the composition is in a range of from about 5:1 to about 250:1.Subset Embodiments include those wherein the Si:Al ratios ranges fromabout 4:1 to about 5:1, from about 5:1 to about 10:1, from about 10:1 toabout 15:1, from about 15:1 to about 20:1, from about 20:1 to about25:1, from about 25:1 to about 30:1, from about 30:1 to about 50:1, fromabout 50:1 to about 100:1, from about 100:1 to about 250:1, from about250:1 to infinity, or a combination of two or more of these ranges.

Embodiment 17

The process of any one of Embodiments 1 to 16, wherein the compositionfurther comprises aqueous HF.

Embodiment 18

The process of any one of Embodiments 1 to 16, wherein the compositionfurther comprises aqueous hydroxide, for example sodium hydroxide,potassium hydroxide, lithium hydroxide, cesium hydroxide, rubidiumhydroxide, barium hydroxide, calcium hydroxide, or magnesium hydroxide.

Embodiment 19

The process of Embodiment 17, wherein the ratio of imidazolium cation:Siis in a range of from about 0.0.2:1 to about 1:1, preferably about0.5:1.

Embodiment 20

The process of Embodiment 18, wherein the ratio of imidazolium cation:Siis in a range of from about 0.05 to about 1:1, preferably about 0.2:1.

Embodiment 21

The process of Embodiment 17 or 19, wherein the ratio of water:Si is ina range of from about 2:1 to about 20:1, preferably in a range of fromabout 4:1 to about 10:1.

Embodiment 22

The process of Embodiments 18 or 20, wherein the ratio of water:Si is ina range of from about 2:1 to about 40:1, preferably in a range of fromabout 15-20:1.

Embodiment 23

The process of any one of Embodiments 1 to 22, wherein thehydrothermally treating is done at a temperature in a range of fromabout 100° C. to about 200° C., preferably about 140° C. to about 180°or from about 160° C. to about 180° C., for a time effective forcrystallizing the crystalline microporous solid.

Embodiment 24

The process of any one of Embodiments 1 to 23, further comprisingisolating a crystalline microporous solid.

Embodiment 25

The process of Embodiment 24, wherein the crystalline microporous solidcontains a portion of the imidazolium cation or linked pair ofquaternary imidazolium cations used in its preparation.

Embodiment 26

The process of Embodiment 20 or 23, further comprising calcining thecrystalline microporous solid at a temperature in a range of from about25° C. to about 850° C. under oxidative (e.g., air, oxygen, or ozone) orinert atmosphere. When a strongly oxidizing atmosphere is uses (e.g.,ozone), the temperature is generally in a range from about 25° C. toabout 200° C. Otherwise, the calcining is done at at least onetemperature in at least one temperature range of from about 350° C. toabout 450° C., from about 450° C. to about 550° C., from about 550° C.to about 650° C., from about 650° C. to about 750° C., from about 750°C. to about 850° C.

Embodiment 27

The process of Embodiment 26, further comprising treating the calcinedmaterial with an aqueous ammonium salt.

Embodiment 28

The process of Embodiment 26, further comprising treating at least somepores of the microporous solid with at least one type of transitionmetal or transition metal oxide

Embodiment 29

A composition comprising:

(a) at least one source of a silicon oxide, germanium oxide, orcombination thereof;

(b) a linked pair of quaternary imidazolium cations of a structure:

wherein t is 3, 4, 5, or 6; and

R is independently methyl or ethyl, and n is independently 1, 2, or 3;

said linked pair of quaternary imidazolium cations having associatedfluoride or hydroxide ions; and

(c) optionally a compositionally consistent crystalline microporoussilicate solid. In some of these embodiments, a portion of the linkedpair of imidazolium cations is occluded in the pores of the crystals

Preferably, the linked pair of quaternary imidazolium cations has astructure of:

and said linked pair of quaternary imidazolium cations having associatedhydroxide ions.

Embodiment 30

The composition of claim 29, further comprising at least one source ofaluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconiumoxide, or combination or mixture thereof. A subset of this embodimentincludes that where the at least one source of aluminum oxide isnecessarily present.

Embodiment 31

A composition comprising:

(a) at least one source of a silicon oxide, germanium oxide, orcombination thereof; and optionally

(b) a source of aluminum oxide; and

(c) an imidazolium cation comprising methyl and ethyl groups and havinga C/N+ ratio in a range of from about 6:1 to 10:1, preferably from 6:1,from 7:1, or from 8:1 to 9:1, more preferably 8:1, such that theimidazolium cation has, for example,

-   -   (i) 3, 4, or 5 methyl groups or    -   (ii) 2, 3, or 4 methyl groups and one ethyl group and

(c) a hydroxide or fluoride anion, preferably substantially free ofother halide counterions, i.e., bromide, chloride, or iodide; and

(d) optionally a compositionally consistent crystalline microporousaluminosilicate solid. This compositionally crystalline microporousaluminosilicate solid may independently have an RTH, HEU, or CIT-17topology, the specific nature of which depends on the target crystallinemicroporous composition. In some of these embodiments, a portion of theimidazolium cation is occluded in the pores of the crystals. Additionalsubsets of this Embodiment include those where only at least one sourceof a silicon oxide is present and those where at least one source ofsilicon oxide and at least one source of aluminum oxide are present.

Embodiment 32

The composition of Embodiment 31, further comprising a source of boronoxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titaniumoxide, indium oxide, vanadium oxide, zirconium oxide, or combination ormixture thereof.

Embodiment 33

The composition of Embodiment 31 or 32, wherein the imidazolium cationis described by a resonance form that is:

Embodiment 34

The composition of any one of Embodiments 29 to 33, wherein the sourceof silicon oxide comprises an alkoxide, hydroxide, or oxide of silicon,or combination thereof.

Embodiment 35

The composition of any one of Embodiments 30 to 34 wherein the source ofaluminum oxide comprises an alkoxide, hydroxide, or oxide of aluminum,an aluminum siloxide, or combination thereof.

Embodiment 36

The composition of any one of Embodiments 29 to 35, wherein the sourceof silicon comprise a silicon alkoxide having an empirical formula ofSi(OR)₄, where R is an alkyl group of 1-6 carbon atoms.

Embodiment 37

The composition of any one of Embodiments 30 to 36, wherein the sourceof aluminum comprise an aluminum alkoxide having an empirical formula ofAl(OR)₃, where R is an alkyl group of 1-6 carbon atoms.

Embodiment 38

The composition of any one of Embodiments 29 to 37, wherein thecomposition further comprises aqueous HF.

Embodiment 39

The composition of any one of Embodiments 29 to 37, wherein thecomposition further comprises aqueous hydroxide.

Embodiment 40

The composition of Embodiment 38, wherein the ratio of imidazoliumcation:Si is in a range of from about 0.2:1 to about 1:1, preferablyabout 0.5:1.

Embodiment 41

The composition of Embodiment 39, wherein the ratio of imidazoliumcation:Si is in a range of from about 0.05 to about 1:1, preferablyabout 0.2:1.

Embodiment 42

The composition of Embodiment 38 or 40, wherein the ratio of water:Si isin a range of from about 2:1 to about 20:1, preferably 4:1 to 10:1.

Embodiment 43

The process of Embodiments 39 or 41, wherein the ratio of water:Si is ina range of from about 2:1 to about 40:1, preferably in a range of fromabout 15:1 to 20:1

Embodiment 44

The composition of any one of Embodiments 30 to 43 wherein the ratio ofSi:Al in the composition is in a range of from about 5:1 to about 250:1.

Embodiment 45

The composition of any one of Embodiments 29 to 44, which is a gel.

Embodiment 46

The composition of any one of Embodiments 29 to 45, furtherindependently comprising a crystalline microporous solid having RTH,HEU, CIT-7 or IWV topology.

Embodiment 47

The composition Embodiment 46, wherein the microporous solid having RTH,HEU, CIT-7, or IWV topology has a Si:Al ratio in a range of at least 5.Note that an Si:Al ratio of infinity (∞) corresponds to a silicatecomposition substantially free of Al.

Embodiment 48

The composition of Embodiment 46 or 47, that is substantially free ofother crystalline materials.

Embodiment 49

A crystalline microporous solid prepared by the process of any one ofEmbodiments 1 to 28. A subset of this Embodiment includes those calcinedcrystalline microporous solid, prepared by a process of any one ofEmbodiments 26 to 28. Another subset of this Embodiment includes thosecompositions, whether prepared by or independent of one of theseprocesses, where the ratio of Si:Al is in a range of from about 4:1 to5:1, from about 5:1 to about 7.3:1, from about 7.3:1 to about 10:1, fromabout 10:1 to about 12.3:1, from about 12.3:1 to about 15:1, from about15:1 to about 17.3:1, from about 17.3:1 to about 20:1, from about 20:1to about 25:1, from about 25:1 to about 50:1, from about 50:1 to about75:1, from about 75:1 to about 100:1, from about 100:1 to about 250:1,from about 250:1 to ∞:1, or a combination of two or more of theseranges, whether as-synthesized, calcined, doped, or otherwise modified.

Embodiment 50

The crystalline solid of Embodiment 49, the crystalline microporoussolid independently having an RTH, HEU, CIT-7 or IWV topology.

Embodiment 51

A crystalline microporous solid of claim 49 or 50 having pores at leastsome of which are occluded with a linked pair of quaternary imidazoliumcations of a structure:

wherein t is 3, 4, 5, or 6, preferably 4 or 5;

R is independently methyl or ethyl, and n is independently 1, 2, or 3;or any of the more specific linked pair of quaternary imidazoliumcations described herein. Depending on the specific conditions used toprepare the solid, the crystalline solid has an RTH, HEU, CIT-7, or IWVtopology, as described herein.

Embodiment 52

A crystalline microporous solid of claim 49 or 50 having pores, at leastsome of which are occluded with an organic complex comprising (a) animidazolium cation comprising methyl and ethyl groups and having a C/N+ratio in a range of from about 6:1 to 10:1, preferably from 6:1, from7:1, or from 8:1 to 9:1, more preferably 8:1, and where the crystallinemicroporous solid has an RTH, HEU, CIT-7, or IWV topology, depending onthe specific conditions used to prepare the solid as described herein.

Embodiment 53

The crystalline microporous solid of Embodiment 51 or 52, wherein theoccluded imidazolium cation or linked pair of quaternary imidazoliumcations is described by a resonance form that is:

Embodiment 54

The crystalline microporous solid of any one of Embodiments 51 to 53,wherein the crystalline solid is a microporous silicate solid.

Embodiment 55

The crystalline microporous solid of any one of Embodiments 51 or 54,wherein the crystalline solid is a microporous aluminosilicate solidhaving a ratio of Si:Al in a range of from about 5:1 to about 250:1.Subsets of this Embodiments include those where the range is from about4:1 to about 5:1, from about 5:1 to about 10:1, from about 10:1 to about15:1, from about 15:1 to about 20:1, from about 20:1 to about 25:1, fromabout 25:1 to about 30:1, from about 30:1 to about 50:1, from about 50:1to about 100:1, from about 100:1 to about 250:1, from about 250:1 toinfinity, or a combination of two or more of these ranges.

Embodiment 56

A crystalline microporous solid having an RTH structure comprising (a)silicon oxide, germanium oxide, or combination thereof and (b) aluminumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, or zirconium oxide,wherein the molar ratio of (a) to (b) is less than 20, preferably in arange of from about 5 to about 10, from about 10 to about 15, from about15 to less than 20, or a combination of two or more of these ranges,more preferably about 15. One subset of this embodiment is one where thecrystalline microporous solid is an aluminosilicate, where the ratio of(a) to (b) refers to the ratio of Si to Al.

Embodiment 57

A calcined crystalline microporous solid having an RTH structurecomprising (a) silicon oxide, germanium oxide, or combination thereofand (b) aluminum oxide, boron oxide, gallium oxide, hafnium oxide, ironoxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, orzirconium oxide wherein the molar ratio of (a) to (b) is in a range offrom about 5 to about 10, from about 10 to about 15, from about 15 toless than 20, or a combination of two or more of these ranges, morepreferably about 15. One subset of this embodiment is one where thecrystalline microporous solid is an aluminosilicate.

Embodiment 58

An as-synthesized or calcined crystalline microporous solid having anHEU framework topology comprising (a) silicon oxide, germanium oxide, orcombination thereof and (b) aluminum oxide, boron oxide, gallium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, zirconium oxide, or combination thereof, wherein themolar ratio of (a) to (b) is in a range of from about 4 to about 5, fromabout 5 to about 7.3, from about 7.3 to about 10, from about 10 to about12.3, from about 12.3 to about 15, from about 15 to about 17.3, fromabout 17.3 to about 20, or a combination of two or more of these ranges.One subset of this embodiment is one where the crystalline microporoussolid is an aluminosilicate, where the ratio of (a) to (b) refers to theratio of Si to Al.

Embodiment 59

A calcined crystalline microporous solid comprising (a) silicon oxide,germanium oxide, or combination thereof and optionally (b) aluminumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination thereof, having 8-MR and 10-MR pore structures and at leastone of the following characteristics:

(a) the solid exhibits an ²⁹Si MAS spectrum having a plurality ofchemical shifts of about 115.59, about 115.19, 111.2, 109.58, 109.27,108.81, and about 106.735 ppm downfield of a peak corresponding to andexternal standard of tetramethylsilane; or

(c) the solid exhibits an XRD diffraction pattern the same as orconsistent with those shown in FIG. 11, FIG. 12, or FIG. 13A/B. Subsetsof this embodiment include those where the crystalline microporous solidis a silicate, aluminosilicate, or a titanosilicate.

Embodiment 60

A calcined crystalline microporous solid comprising (a) silicon oxide,germanium oxide, or combination thereof and optionally (b) aluminumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination thereof, having cse and mtw building blocks (as shown inFIG. 18 or FIG. 19). Subsets of this embodiment include those where thecrystalline microporous solid is a silicate, aluminosilicate, or atitanosilicate.

Embodiment 61

A calcined microporous solid having a framework substantially asdescribed in Table 11, or an aluminosilicate or titanosilicate versionthereof.

Embodiment 62

A calcined microporous solid having an IWV framework and exhibiting anXRD diffraction pattern the same as or consistent with those shown inFIG. 26A or FIG. 26B.

Embodiment 63

The calcined microporous solid of Embodiment 62, having an Si:Al ratioin a range of from about 4:1 to about 5:1, from about 5:1 to about 10:1,from about 10:1 to about 15:1, from about 15:1 to about 20:1, from about20:1 to about 25:1, from about 25:1 to about 30:1, from about 30:1 toabout 50:1, from about 50:1 to about 100:1, from about 100:1 to about250:1, from about 250:1 to infinity, or a combination of two or more ofthese ranges. Note that an Si:Al ratio of infinity (∞) corresponds to asilicate composition substantially free of Al.

Embodiment 64

The calcined compositions of any one of Embodiments 56 to 61, whereinthe calcined composition is predominantly in the hydrogen form.

Embodiment 65

A crystalline microporous composition comprising (a) silicon oxide,germanium oxide, or combination thereof and (b) aluminum oxide, boronoxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titaniumoxide, indium oxide, vanadium oxide, zirconium oxide, or combinationthereof, and exhibiting a powder X-ray diffraction pattern of any one ofFIG. 2, FIG. 9A or B, FIG. 10, FIG. 11, FIG. 12, FIG. 13A/B, FIG. 26A orB, FIG. 27, FIG. 28, FIG. 29, FIG. 31, or FIG. 32.

Embodiment 66

A crystalline microporous composition comprising (a) silicon oxide,germanium oxide, or combination thereof and (b) aluminum oxide, boronoxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titaniumoxide, indium oxide, vanadium oxide, zirconium oxide, or combinationthereof, and having at least the five major peaks, and optionallyadditional peaks, preferably in order of decreasing relativeintensities, in the powder X-ray diffraction pattern, substantially asprovided in Tables 2A or 2B.

Embodiment 67

A process comprising carbonylating DME with CO at low temperatures,reducing NOx with methane, cracking, dehydrogenating, convertingparaffins to aromatics, MTO, isomerizing xylenes, disproportionatingtoluene, alkylating aromatic hydrocarbons, oligomerizing alkenes,aminating lower alcohols (including methanol), separating and sorbinglower alkanes (e.g., C3-C6 alkanes, hydrocracking a hydrocarbon,dewaxing a hydrocarbon feedstock, isomerizing an olefin, producing ahigher molecular weight hydrocarbon from lower molecular weighthydrocarbon, reforming a hydrocarbon, converting a lower alcohol orother oxygenated hydrocarbon to produce an olefin products, reducing thecontent of an oxide of nitrogen contained in a gas stream in thepresence of oxygen, or separating nitrogen from a nitrogen-containinggas mixture by contacting the respective feedstock with the crystallinemicroporous solid of any one of Embodiments 49 or 56 to 65 underconditions sufficient to affect the named transformation.

Embodiment 68

A method comprising contacting methanol with a composition of any one ofclaims Embodiments 49 or 56 to 65 under conditions sufficient to convertthe methanol to at least one type of olefin.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees Celsius, pressure is ator near atmospheric.

Example 1. Materials and Methods

Unless otherwise noted all reagents were purchased from Sigma-Aldrichand were used as received. Hydroxide ion exchanges were performed usingSupelco Dowex Monosphere 550A UPW hydroxide exchange resin with anexchange capacity of 1.1 meq/mL. Titrations were performed using aMettler-Toledo DL22 autotitrator using 0.01 M HCl as the titrant. Allliquid NMR spectra were recorded with a 400 MHz Varian Spectrometer.

The ¹³C CP-MAS NMR spectra were recorded using a Bruker Avance 200 MHzspectrometer with a 7 mm rotor at a spinning rate of 4 kHz and wereconducted in a 4.7 T magnetic field, corresponding to Larmor frequenciesof 200 MHz and 50.29 MHz for ¹H and ¹³C respectively. The ¹³C spectraare referenced to adamantane as a secondary external standard relativeto tetramethylsilane. ²⁹Si and ¹⁹F NMR were performed using a BrukerDSX-500 spectrometer (11.7 T) and a Bruker 4 mm MAS probe. The spectralfrequencies were 500.2 MHz, 99.4 MHz, and 470.7 MHz for ¹H, ²⁹Si, and¹⁹F nuclei, respectively, and spectra were referenced to externalstandards as follows: tetramethylsilane (TMS) for ¹H and ²⁹Si, and CFCl₃for ¹⁹F. The ²⁷Al MAS NMR were recorded using a Bruker AM 300 MHzspectrometer with a 4 mm rotor at a spinning rate of 8 kHz, and wereconducted in a 7.0 T magnetic field corresponding to a Larmor frequencyof 78.172 MHz. The ²⁷Al spectra are referenced to 1.1 M Al(NO₃)₃ as anexternal standard.

Thermogravimetric analysis measurements were performed with a NetzschSTA 449C Jupiter. Samples were heated in air to 900° C. at a rate of 1°C./min. All Argon adsorption isotherms were performed at 87.45 K using aQuantachrome Autosorb iQ and were conducted using a quasi-equilibrium,volumetric technique. All powder X-ray diffraction (PXRD)characterization was conducted on a Rigaku MiniFlex II with Cu K_(α)radiation. Scanning electron micrograph (SEM) images were acquired on aZEISS 1550 VP FESEM, equipped with in-lens SE. EDS spectra were acquiredwith an Oxford X-Max SDD X-ray Energy Dispersive Spectrometer system.

Diffuse reflectance UV-visible (DRUV) spectra (for CIT-7) were recordedusing a Cary 3G spectrophotometer equipped with a diffuse reflectancecell; zeolite samples were calcined prior to data collection.Three-dimensional electron diffraction data were collected on 2 crystalsof CIT-7 using the rotation electron diffraction (RED) technique ofZhang (D. Zhang, P. Oleynikov, S. Hovmöller and X. Zou, Z. Kristallogr.,2010, 225, 94-102) and Wan (W. Wan, J. Sun, J. Su, S. Hovmöller and X.Zou, J. Appl. Cryst., 2013, 46, 1863-1873). The RED software wasinstalled on a JEOL 2010 microscope operating at 200 kV, and data werecollected over a tilt range of ±55° with a tilt step of 0.50° for thefirst set and 0.35° for the second set, the exposure time is 3 secondsper tilt step.

Example 2. Synthesis of Imidazolium Cations Example 2.1

Pentamethylimidazolium hydroxide was synthesized as shown in thefollowing Scheme.

Pentamethylimidazolium was synthesized by dissolving1,2,4,5-tetramethylimidazole (TCI Chemicals) in methanol and thencooling in a dry ice bath. A three-fold molar excess of iodomethane(Aldrich) was then slowly added (Caution: Highly exothermic reaction!)and the mixture was then slowly warmed to room temperature and stirredfor one day. The solvent and excess iodomethane were then removed usingrotary evaporation (Caution: Highly toxic vapors present, useappropriate precautions) and the product was recrystallized from acetoneand washed with ether. The structure was verified using ¹H and ¹³C NMR(D₂O, methanol added as internal standard) and the product was convertedfrom the iodide to the hydroxide form using hydroxide exchange resin inwater and the product was titrated using a Mettler-Toledo DL22autotitrator using 0.01 M HCl as the titrant. ¹H-NMR (500 MHz, D₂O): δ3.60 (s, 6H), 2.54 (s, 3H), 2.20 (s, 6H). ¹³C-NMR (125 MHz, D2O): δ7.99, 9.76, 31.58, 125.42, 142.21.

Example 2.2. Syntheses of Other Organic Structure Directing Agents(OSDAs)

Reaction Type 1:

The parent imidazole was dissolved in methanol and then cooled in a dryice/acetone bath. Then a three-fold molar excess of methyl iodide wasslowly added. (Caution: These reactions can be highly exothermic, useappropriate precautions.) The mixture was then allowed to slowly warm toroom temperature and finally refluxed overnight. After cooling thesolvent and excess methyl iodide were removed using rotary evaporation(Caution: Highly toxic vapors present, use appropriate precautions), andthe product was recrystallized from acetone and washed with ether.

Reaction Type 2:

The parent imidazole was dissolved in chloroform and then a two-foldmolar excess of potassium carbonate was added. The mixture was cooled ina dry ice/acetone bath and then a four-fold molar excess of methyliodide was slowly added. (Caution: These reactions can be highlyexothermic, use appropriate precautions.) The mixture was then allowedto slowly warm to room temperature and finally refluxed overnight. Aftercooling to room temperature the potassium carbonate was filtered off andthe solids were rinsed with extra chloroform to recover all the product.Then the solvent and excess methyl iodide were removed using rotaryevaporation (Caution: Highly toxic vapors present, use appropriateprecautions), and the product was recrystallized from acetone and washedwith ether.

In both types of reactions the structure was verified using ¹³C NMR inD₂O with methanol added as an internal standard. The products were thenconverted from iodide to hydroxide form using hydroxide exchange resin(Dowex Marathon A, hydroxide form) in water, and the product wastitrated using a Mettler-Toledo DL22 autotitrator using 0.01 M HCl asthe titrant.

TABLE 3 Syntheses and Characterizations of Imidazolium StructureDirecting Agents Reaction Organic Parent Imidazole Supplier Type ¹³C NMRδ (ppm) 1 N-methylimidazole Aldrich 1 36.32, 123.76, 136.86 21,2-Dimethylimidazole Aldrich 1 8.52, 34.48, 121.64, 144.63 34-methylimidazole Aldrich 2 8.52, 33.37, 35.87, 120.37, 132.33, 135.86 42-ethylimidazole Aldrich 2 9.92, 16.59, 34.71, 122.07, 148.16 52,4-dimethylimidazole Synquest 2 8.62, 9.38, 31.46, 34.36, 118.64,130.14, 143.89 6 2-ethyl-4-methylimidazole Aldrich 2 8.80, 10.17, 16.93,31.52, 34.36, 118.83, 120.23, 130.23, 147.32 7 2-isopropylimidazole TCI2 17.55, 24.79, 35.68, 122.65, 149.69 8 1,2,4,5-tetramethylimidazole TCI1 7.99, 9.76, 31.58, 125.42, 142.21

The linked quaternary imidazolium cation OSDAs used in this work weresynthesized by reacting 200 mmol of 1,2,4,5-tetramethylimidazole (TCIChemicals) with 100 mmol of either 1,5-dibromopentane,1,4-dibromobutane, or 1,3-dibromopropane (all from Aldrich) at reflux inmethanol overnight. The solvent was then removed using rotaryevaporation and the product washed with ether. The products wereverified using ¹³C NMR in D₂O with methanol added as an internalstandard. ¹³C-NMR (125 MHz, D₂O), pentane linked pentamethyl imidazoliumcations: δ 7.76, 7.82, 9.61, 22.82, 28.58, 31.42, 44.72, 124.84, 126.03,141.95. ¹³C-NMR (125 MHz, D₂O), butane linked pentamethyl imidazoliumcations: δ 7.56, 9.35, 25.88, 30.17, 21.21, 44.14, 124.60, 126.00,141.89. HRMS-FAB (m/z): [M+H] calculated for C₁₈H₃₁N₄, 303.25. found,303.26. The products were ion exchanged and titrated as described above.

Example 3.1. General Methods for Preparation of Crystalline MicroporousSilicate or Aluminosilicate Solids Using Imidazolium Cations

The following general synthesis procedures were used in the preparationof the microporous materials can be found below. In all situations wherea rotating oven was used the samples were spun at 63 rpm. All powderx-ray diffraction characterization was conducted on a Rigaku MiniFlex IIwith Cu Kα radiation.

Example 3.2. Fluoride Mediated Reactions

A general procedure for a fluoride mediated synthesis was as follows.Tetraethylorthosilicate (TEOS) and aluminum isopropoxide (if necessary)were added to the OSDA in its hydroxide form in a Teflon Parr reactorliner. The container was closed and stirred for at least 12 hours toallow for complete hydrolysis. The lid was then removed and the alcoholand appropriate amount of water were allowed to evaporate under a streamof air. The composition was monitored gravimetrically. Additional waterwas added as necessary, and then aqueous HF (Aldrich) was added and themixture was stirred by hand until a homogenous gel was obtained.(Caution: Use appropriate personal protective equipment, ventilation andother safety measures when working with HF.) In some cases, the finalmolar ratios of the gel were:(1−x)SiO₂ :xAl:0.5ROH:0.5HF:yH₂O.

In those experiments involving pure silica gels or gels evaluating OSDAsother than pentamethyl imidazolium hydroxide in RTH syntheses, the finalgel molar ratios were:1SiO₂:0.5ROH:0.5HF:xH₂O, x=4,70.95SiO₂:0.05Al:0.5ROH:0.5HF:4H₂O

In other cases where the final compositions were Si/Al=15 (i.e., informing the CIT-7 compositions), the final molar ratios were:1SiO₂:0.0333Al:0.08Na₂O:0.16ROH:30H₂O

The parameters x and y were varied depending on the synthesis and thedesired composition. For low water syntheses, a final evaporation stepwas used after the addition of HF to reach the desired water ratio. TheTeflon-lined Parr reactor was sealed and placed in a rotating oven at160° C. or 175° C. Aliquots of the material were taken periodically byfirst quenching the reactor in water and then removing enough materialfor powder X-ray diffraction (PXRD).

Example 3.3. Hydroxide Mediated Reactions

For the hydroxide syntheses, several variations on gel Si/Al as well asthe sources of silica and alumina were used. Specific synthesispreparations are below. For all hydroxide reactions, seeds were addedafter 1 day at reaction temperature, once a decrease in pH was observed.Normally seeds were added as a homogeneous aliquot of the contents of aprevious, completed reaction (less than 0.3 mL) as these were found tobe more active than seeds that had been washed. The use of seeds wasfound to speed the formation of RTH and to help avoid the formation ofdense phases, but this influence was not extensively investigated.Aliquots were taken periodically, and crystallization was monitored byboth PXRD and pH, as an increase in pH was generally observed when theproduct crystallized. After the product crystallized, the material waswashed with DI water and then collected via centrifugation. This processwas repeated at least three times, and a final wash was performed usingacetone. The product was dried at 100° C. in air.

Example 3.4. Sodium Aluminate (or Reheiss F-2000) and Ludox AS-40 (orCabosil)

The OSDA in its hydroxide form, sodium hydroxide (if necessary), anynecessary water and sodium aluminate (Pfaltz & Bauer) were combined in aTeflon Parr reactor liner and stirred until the sodium aluminatecompletely dissolved. Ludox AS-40 (Aldrich) was then added and stirreduntil a homogenous gel was obtained. In sodium-free syntheses, ReheissF-2000 (55 wt % Al₂O₃) was used as the source of aluminum instead ofsodium aluminate, and Cabosil M-5 was used instead of Ludox AS-40. Thegel pH was measured, and then the Teflon-lined Parr reactor was placedin a rotating oven at 160° C.

Example 3.5. Si/Al=15 (NH₄—Y and Sodium Silicate)

Following the method of Wagner et al., J. Am. Chem. Soc. 2000, 122, 263,2 mmol of the OSDA in its hydroxide form was mixed with 0.20 g of 1 MNaOH, and water was added to give a total mass of 6 g. Then 2.5 grams ofsodium silicate (PQ Corporation, 28.6 wt % SiO₂ and 8.9 wt % Na₂O) wasadded to the mixture and finally 0.25 g of NH₄—Y (Zeolyst CBV 500,Si/Al=2.55) was added. The solution was heated at 140° C. in a rotatingoven.

Example 3.6. Si/Al=15 (CBV 720)

3 mmol of the OSDA in its hydroxide form was mixed with 1 g of 1 M NaOHand water was added to bring the total mass to 7 g. Then 1 g of CBV 720(Zeolyst, Si/Al=15) was added. The solution was heated at 175° C. in arotating oven.

Example 3.7. Si/Al=30 (CBV 760)

3 mmol of the OSDA in its hydroxide form was mixed with 1 g of 1 M NaOHand water was added to bring the total mass to 7 g. Then 1 g of CBV 760(Zeolyst. Si/Al=30) was added. The solution was heated at 175° C. in arotating oven.

Example 3.8. SSZ-13 Synthesis

SSZ-13 was synthesized using a standard method of Robson, H. Verifiedsynthesis of zeolitic materials; 2001. In a typical preparation, 3.33 gof 1 M NaOH was mixed with 2.81 g of N,N,N-trimethyl-1-adamantammoniumhydroxide (Sachem, 1.18 mmol OH/g) and 6.62 g of water. Then 0.077 g ofReheiss F-2000 (55 wt % Al₂O₃) was added and stirred until the solutioncleared. Finally, 1.00 g of Cabosil M-5 was added and stirred until ahomogeneous solution was obtained. The solution was heated at 160° C. ina rotating oven for approximately 6 days.

Example 3.9. SAPO-34 Synthesis

SAPO-34 was prepared from the following gel composition: 0.5(TEA)₂O:1.5Pr₂NH:0.6 SiO₂:1Al₂O₃:1P₂O₅:70H₂O. In a typical preparation, 11.5 g of85 wt % phosphoric acid were dissolved in 4.35 g of water and stirredfor 5 minutes. Then 6.875 g of Catapal B alumina were added to 20 g ofwater and stirred for 10 minutes. The mixtures were then slowly combinedand stirred for 1 hour at room temperature. Next 4.48 g of Ludox HS-40was added and stirred by hand until a homogenous gel was obtained. Then20.8 g of 35 wt % TEAOH and 7.61 g of dipropylamine were added and thegel was homogenized by manual stirring. Then the gel was stirred at roomtemperature for 2 hours. Finally, the gel was added to a Teflon-linedParr reactor and heated at 200° C. without stirring for 24 hours.

Example 3.10. Si/Al=50 (Ludox AS-40 and Sodium Aluminate)

4 mmol of the OSDA in its hydroxide form was mixed with 1.56 g of 1 MNaOH and the total mass was brought to 9.66 g with the addition ofwater. Then 0.038 g of sodium aluminate (Pfaltz & Bauer) was added andstirred until dissolved. Finally 3 g of Ludox AS-40 was added andstirred until a homogeneous gel was obtained. Seeds were added and thenthe gel was heated at 160° C. in a rotating oven.

Example 3.11

Tosoh 390HUA Reaction: Following the method of Zones et al., Chem.Mater., 26 (2014) 3909-3913, 3 mmol of the OSDA in its hydroxide formand 0.75 g of 1 M KOH were added to a Teflon Parr Reactor. Then 0.92 gof Tosoh 390HUA was added (highly dealuminated FAU with Si/Al˜250) andthe mixture was stirred until homogeneous. The gel was heated at 175° C.in a rotating oven.

Example 3.12. Calcination

All products were calcined in breathing grade air. The material washeated to 150° C. at 1° C./min under flowing air, held for three hours,then heated to 580° C. at 1° C./min and held for 6-12 hours underflowing air to assure complete combustion of the organic.

Example 4. Reaction Testing of RTH Materials

Prior to reaction testing, all materials were calcined as describedabove. After calcination they were exchanged to ammonium form using 1 MNH₄NO₃ (100 mL of solution per gram of catalyst) at 95° C. with stirringfor three hours, this was done a total of three times per sample. Afterammonium exchange the materials were washed with water and dried andthen calcined. The calcined materials were then pelletized, crushed, andsieved. Particles between 0.6 mm and 0.18 mm were supported betweenglass wool beds in an Autoclave Engineers BTRS, Jr. SS-316 tubular,continuous flow reactor.

All catalysts were dried at 150° C. in situ in a 30 cm³/min flow of 5%Ar/95% He for 4 h prior to the reaction. The reactions were conducted at400° C. in a 10% methanol/inert flow. Methanol was introduced via aliquid syringe pump at 5.4 μL/min, into a gas stream of the inert blendat 30 cm³/min. The reactant flow had a weight hourly space velocity of1.3 h⁻¹. In a typical run, 200 mg of dry catalyst was loaded. Effluentgases were evaluated using an on-stream GC/MS (Agilent GC 6890/MSD5793N)with a Plot-Q capillary column installed. Conversions and selectivitieswere computed on a carbon mole basis. Catalyst regeneration betweenreaction tests was done in-situ by exposing the catalyst to breathinggrade air at reaction temperature, ramping to 580° C. at 1° C./min,holding at 580° C. for 6 hours, and then cooling to reactiontemperature.

Example 5. Results

In pure silicate systems, as well as germanosilicate systems, themono-imidazolium cations directed the formation of STW. However, whenaluminum was introduced into the system the product was aluminosilicateRTH. In the initial series of experiments, the reaction conditions werethose shown in Table 4. A representative powder X-ray diffractionpattern of one of the materials obtained is shown in FIG. 1. All peaksmatched those reported for the spectrum for RTH.

TABLE 4 RTH Synthesis Conditions. Experimental Series #1 Si Al R⁺ F⁻ H₂OTemp, ° C. Time, days Results Comments 1 0.02 0.5 0.5 14 160 12 RTH 10.05 0.5 0.5 14 160 12 RTH 1 0.05 0.5 0.5 4 160 10 RTH 1 0.05 0.5 0.5 4160 10 RTH 1 0.05 0.5 0.5 7 160 4 RTH + STW seeds STW added Molar ratiosof materials based on Si = 1 R⁺ refers to pentamethylimidazolium cation

Subsequent experiments were directed to expanding the range ofcompositions (Table 5). In these experiments, it was shown that thefluoride method was able to produce RTH across a wide range ofcompositions, but at the highest Si/Al ratios tested, STW appeared as acompetitive phase (sample F9). The crystal sizes and morphologies wereconsistent with pure-silicate RTH produced in fluoride media, and thelarge crystal size was what is generally observed for low-water,fluoride-mediated syntheses. Comparison of ¹³C CP-MAS NMR spectra of theas-synthesized RTH zeolite with a solution spectrum of thepentamethylimidazolium ion in D₂O showed that it was this cation, andnot a decomposition product, that led to the formation ofaluminosilicate RTH. See FIG. 5. In order to determine the coordinationof the aluminum in the material, ²⁷Al MAS NMR was performed on thecalcined sample containing the highest amount of aluminum (sample F2),and the spectrum is shown in FIG. 6. The single resonance in this sampleat 54 ppm is consistent with tetrahedrally coordinated aluminum, andthere is no evidence of octahedrally coordinated aluminum, normallyfound around 0 ppm.

TABLE 5 RTH Synthesis in Fluoride Media. Experimental Series #2 GelSi/Al Product Si/Al* Gel H₂O/SiO₂ Time, days Sample 5 — 7 No product F110 7 7 29 F2 15 10 14 46 F3 20 16 14 22 F4 20 18 4 10 F5 33 22 14 20 F640 26 14 17 F7 50 27 14 20 F8 150 STW impurity 7 7 F9 *Reported Si/Alratio is of calcined materials

The success of using pentamethylimidazolium in fluoride-mediatedreactions to produce aluminosilicate RTH led to work inhydroxide-mediated reactions as well, with seeds of RTH added to promoteits formation. The results of the syntheses are shown in Table 6. Ingeneral, these syntheses were found to be sensitive to reaction time andtemperature, and required careful monitoring to avoid the formation ofdense phases. Seeds of RTH were added to all reactions to promote theformation of RTH, but the exact influence of the seeds was notextensively investigated. A representative PXRD of the calcined materialproduced in hydroxide media is shown in FIG. 2. The crystal sizes of theproducts were generally much smaller in hydroxide syntheses than in thefluoride syntheses, as is shown in FIG. 4A-C. The smaller crystal sizesobserved under these conditions are consistent with what is generallyreported in hydroxide syntheses. It is interesting to note that theaggregation appeared to be different in reactions where no sodium waspresent compared to those with sodium present (FIG. 4A-C). ¹³C CP-MASNMR showed that pentamethylimidazolium was also occluded intact in thematerial prepared in hydroxide media (FIG. 4A-C). ²⁷Al MAS NMR was usedto characterize the sample containing the largest amount of aluminum(sample H1), as was done in the fluoride-mediated case, and is shown inFIG. 6. There is a single resonance at 54 ppm corresponding totetrahedrally coordinated aluminum and no evidence of any significantamount of octahedral aluminum. An argon adsorption isotherm for sampleH4 is shown in FIG. 7, and the micropore volume was calculated to be0.16 cm³/g (t-plot method). The EDS analyses of the materialssynthesized in hydroxide media are given in Table 6, and the resultsshow that RTH can be crystallized across a wide range of compositionsfrom Si/Al of 6 to 59 in the calcined product (a large expansion overpreviously reported results). Of significant interest are the low-silicasyntheses (the lowest product found was Si/Al=6, sample H1), much lowerthan any other reported compositions.

TABLE 6 RTH Synthesis in Hydroxide Media. Experimental Series #3 GelProduct Gel Gel Gel Time, Si/Al Si/Al^(a) Na/Si ROH/Si H₂O/Si daysSample  5^(b) 6 0.16 0.16 30 10 H1 10^(b) 9 0.16 0.16 30 10 H2 15^(c) 99 H3 15^(b) 14 0.16 0.16 30 10 H4 15^(d) 15 0.32 30 15 H5 15^(e) 17 10H6 20^(b) 20 0.16 0.16 30 12 H7 30^(f) 29 13 H8 50^(b) 45 0.10 0.20 30 9H9 75^(b) 59 0.10 0.20 30 9 H10 ^(a)Reported Si/A1 ratio is of calcinedmaterial; ^(b)Made with Ludox AS-40 and sodium aluminate; ^(c)Made withNH₄-Y and sodium silicate; ^(d)Made using Cabosil M-5 and ReheissF-2000; ^(e)Made using CBV 720 as only source of Si and Al; ^(f) Madeusing CBV 760 as only source of Si and Al.

Example 6. Reaction Testing

The catalytic activity of RTH for the MTO reaction was evaluated usingthree different samples of RTH prepared in hydroxide media at differentSi/Al ratios, and the results were compared to samples of SSZ-13 andSAPO-34. The samples of RTH tested were prepared using the CBV 720, CBV760 and the sodium aluminate and Ludox synthesis routes, with productSi/Al values of 17, 29 and 59, respectively (samples H6, H8, H10). Thesample of SSZ-13 had a product Si/Al of 19. The MTO reaction data forthe SSZ-13 and SAPO-34 are given in FIG. 8A and FIG. 8B, for the RTHmaterials is given in FIG. 8C-G.

The propylene to ethylene ratio was much higher for RTH than SSZ-13 orSAPO-34. In sample H6 with Si/Al=17, the maximum propylene to ethyleneselectivity ratio observed was 3.6 at 96 minutes on stream. For sampleH8 with Si/Al=29, the maximum propylene to ethylene selectivity ratioobserved was 3.9 at 96 minutes on stream. For sample H10 with Si/Al=59,the maximum propylene to ethylene selectivity ratio observed was 3.6between 25 and 41 minutes on stream. These selectivity ratios are muchhigher than those observed with SSZ-13 or SAPO-34, where the maximumpropylene to ethylene ratios are 1.7 at 96 minutes on stream and 1.3across several time points, respectively (FIGS. 8A and 8B). This resultshows that RTH would be a superior catalyst in applications where ahigher propylene to ethylene ratio is desired.

The selectivity towards butene was also higher for RTH than for SSZ-13or SAPO-34. The maximum selectivities to butene for the RTH samples were0.22, 0.27 and 0.25 for the samples with Si/Al=17, 29 and 59,respectively (H6, H8, H10). The highest selectivity observed for SSZ-13was 0.15 and for SAPO-34 was 0.17 (FIGS. 8A and 8B).

With the RTH samples, one of the main differences between the sampleswas the selectivity to C₁-C₄ saturates (mainly propane). The maximumselectivity for each sample occurred at the first time point, and thevalues were 0.39, 0.28 and 0.19 for the samples with Si/Al=17, 29 and59, respectively (samples H6, H8, H10). It was also observed that timeon stream with complete methanol conversion decreased with increasingSi/Al ratios.

When comparing RTH to SSZ-13 or SAPO-34, one of the main differencesobserved was the time on stream until the catalyst deactivated. In allthe RTH samples, this was significantly less than it was for eitherSSZ-13 or SAPO-34. However, an industrial scale MTO reaction will likelybe run in a fluidized-bed reactor, which allows continuous regenerationof the catalyst. This will allow a system to be operated at any timepoint along a fixed bed reactor profile, assuming the catalyst can beregenerated. To this end, the ability of RTH to be regenerated wastested by running the Si/Al=17 material (sample H6) for threeconsecutive MTO reaction runs with regeneration between each run, andthe results are given in FIGS. 8C-D. There are some small differencesbetween the fresh catalyst (FIG. 8C) and first regeneration of thecatalyst (FIG. 8D), but the MTO reaction behavior is similar between thefirst regeneration (FIG. 8D) and second regeneration (FIG. 8E) of thematerial. The regeneration experiment demonstrates that RTH would besuitable for use in fluidized bed systems as it can maintain itsactivity across multiple regeneration cycles.

Example 7. Testing Additional Imidazolium Cations Example 7.1. Synthesesof Aluminosilicate RTH

Results of the imidazolium screening reactions are given in Table 7. Itwas found that nearly all of the imidazolium screened in this study ledto the formation of RTH. The simplest imidazolium OSDA, 1, did notproduce RTH and was found to decompose under many of the conditionstested in this study. It was found to produce materials in fluoridemediated reactions, consistent with those previously reported, so theinstability is property of the organic. Additionally, OSDA 7 was alsounstable under many of the conditions tested in these screeningreactions, and was not found to lead to RTH under any conditions tested.

All of the other OSDAs tested were able to produce aluminosilicate RTHunder a majority of the inorganic conditions tested. The formation ofaluminosilicate RTH using pentamethylimidazolium was first observed influoride-mediated aluminosilicate conditions, and OSDAs 2-6, 8 were allable to produce RTH under this condition, without the use of seeds.Under more conventional, hydroxide-mediated conditions, they were alsoobserved to form RTH across a wide compositional range. In some cases,such as with OSDAs 2-4 the use of seeds was found to be necessary tocause the formation of RTH. This suggests that these organics were lessdirecting to RTH, but are still able to form the material whennucleation is induced through seeding. The OSDAs found to be the moststrongly directing to RTH were 2, 5 and 8.

Example 7.2. Pure-Silica RTH

None of the mono-quat imidazolium examined in this study was able toproduce pure-silica RTH. The only previously reported method to makethis material uses a difficult to produce OSDA (see Background, above).Recent investigations by the present inventors have examined linkedpairs of quaternary imidazolium cations (“diquats”) produced usingtetramethylimidazole. The diquat with a 5-carbon linker in low-water,fluoride-mediated reactions was found to produce pure-silica RTH atH₂O/Si₂O=4, in competition with BEA, STW and CIT-7. From the as-madematerial. FIG. 9, lower trace) it was not obvious that the materialproduced is RTH, this was only apparent upon calcination. Initially, itwas thought that the RTH was formed through topotactic condensation.This was tested by treating the material in ozone at 150° C., below thetemperature at which topotactic condensation is reported to occur, whichis above 500° C. Under these conditions the formation of RTH was alsoapparent, and the similarity of the as-made and calcined PXRD samplessuggests that it is likely that the PXRD of the as-made material was dueto the organic phase. This is only the second report of pure silica RTHand in this method the organic is accessible in only a single step.

TABLE 7 Results of various microporous materials syntheses. Pure Si PureSi Tosoh fluoride, fluoride, Si/Al = 390, H₂O/ H₂O/ Si/Al = Si/Al = 15CBV720, CBV720, CBV760, CBV760, 175° C., Num- SiO2 = 4, SiO2 = 7, 20 15no 160° C., 160° C., 175° C., 175° C., Si/Al = no Organic ber 175° C.175° C. fluoride Seeds seeds seeds no seeds seeds no seeds 50 seedsseeds

1 TON TON FER OD OD OD TON TON ZSM- 48 + D

2 ITW ITW RTH RTH RTH RTH RTH OD RTH D

3 ITW ITW RTH RTH MOR OD OD TON OD TON ZSM- 48

4 CIT-7, ITW, STW, STF, MTW ITW RTH RTH RTH RTH OD OD OD MTW D

5 STW STW RTH RTH RTH + MOR RTH RTH RTH RTH D

6 STW HPM-2 RTH RTH MOR + RTH OD OD OD OD MTW D

7 STF ?? ?? MOR MOR OD OD OD

8 STW STW RTH RTH RTH RTH RTH RTH RTH RTH D OD = Organic Decomposed A =Material was still amorphous after 30 days but it was not apparent thatthe organic had degraded. D = Dense Phase ?? Product could not beidentified

Example 8.1. Investigations into the Preparation of CIT-7

The OSDAs used to produce CIT-7 were 2-ethyl-1,3-dimethylimidazolium (1)and 3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium) (2)and are shown as:

The synthesis and characterization details for these OSDAs can be foundin Example 1.

A wide range of products could be produced with the2-ethyl-1,3-dimethylimidazolium cation in fluoride-mediate, pure-silicareactions depending on the specific inorganic conditions used such asH₂O/SiO₂ ratio and temperature. Results of syntheses over a wide rangeof conditions are given in Table 8.

TABLE 8 Pure-silica fluoride-mediated syntheses using2-ethyl-1,3-dimethylimidazolium cation H₂O/SiO₂ Temperature (° C.)Result 2 140 Unknown 4 140 STF 7 140 Amph 14 140 Amph 2 160 ITW 4 160STW + ITW 7 160 ITW + MTW 14 160 ITW 2 175 STW 4 175 Unknown 7 175 ITW14 175 MTW 2 175 STE + CIT-7 + ITW 2.5 175 CIT-7 3 175 CIT-7 3.5 175ITW + CIT-7 4 (13 separate trials)^(a) 175 CIT-7 + ITW 4.5 175 CIT-7 +STW 5 175 ITW + Unknown 6 175 Pending Unknown means products could notbe identified. In reactions with multiple products phase mixtures werefound but relative amounts were not quantified ^(a)Seeds of CIT-7 wereadded

Many known products emerged in these syntheses such as ITW, MTW, STF andSTW as well as a few products that could not be characterized. Inparticular at low H₂O/SiO₂ ratios at 175° C. a phase was identifiedusing powder x-ray diffraction (XRD) that was not a known microporousmaterial phase. However, this phase was typically found as a phasemixture with either ITW or STW. A representative XRD of a calcined,pure-silica material made with 2-ethyl-1,3-dimethylimidazolium cationcontaining both CIT-7 as well as an ITW impurity is shown in FIG. 10. Itwas found that the use of seeds of CIT-7 helped to avoid the formationof ITW or STW, but it was found to be difficult to avoid the formationof any competing phases. At H₂O/SiO₂=2.5 and 3 it was not possible todetect any impurity phases using XRD, but in general it was difficult tosynthesize a sample of pure CIT-7 using 2-ethyl-1,3-dimethylimidazoliumcation as it is able to form many competing phases.

In addition to these imidazolium based OSDAs, additional studies intothe use of linked pairs of quaternary imidazolium cations, havingdiffering carbon chain lengths between the imidazolium moieties, such asshown here:

have been used in pure-silica, fluoride-mediated syntheses at 175° C.and aluminosilicate, hydroxide-mediated syntheses with Si/Al=15 at 160°C. Representative results for various carbon linker chain lengths aregiven in Table 9.

TABLE 9 Synthesis results using tetramethylimidazolium diquats ofvarying carbon linker length H₂O/ H₂O/ SiO₂ = 4, SiO₂ = 7, Si/Al = 10,Si/Al = 15, Si/Al = 30, Organic 175° C. 175° C. hydroxide hydroxidehydroxide 3 carbon STW Amorphous Amorphous linker 4 carbon CIT-7, STW +IWV linker STW Layered 5 carbon RTH BEA IWV IWV IWV linker 6 carbon BEABEA IWV IWV linkerFor the 4, 5 and 6 carbon linkers in the aluminosilicate hydroxidereactions the IWV framework was found as the product. This framework hasbeen previously reported using dimethyldiphenylphosphonium influoride-mediated, low-water aluminosilicate reactions but takes a longtime to form (49 days) and is known as ITQ-27. See, e.g., U.S. Pat. No.7,527,782. It contains a 2-dimensional channel system of 12-memberedrings that also contains 14-membered rings that are only accessiblethrough 14-membered rings. The present method is simpler, and providesfor a wider range of high Si:Al compositions.

In the pure-silica, fluoride-mediated reactions at 175° C. a widevariety of products have been observed depending on chain-length andwater content (Table 9). Finding BEA as a product in these situations isnot surprising as it has been found to form with similar diquats. See,e.g., A. Jackowski, et al., J. Am. Chem. Soc. 131 (2009) 1092-100. Ofthe other products found in these reactions, STW and RTH have been foundto form with pentamethylimidazolium, the similar nature of these diquatsto pentamethylimidazolium makes these expected results. Using the diquatwith a 4 carbon chain linker (the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium)dication) led to the formation of CIT-7 in the pure silica syntheseswith H₂O/SiO₂=4. In some instances STW was found as a competing phase,but it was simple to direct the formation to pure CIT-7 by adding seedsof CIT-7. A representative XRD of calcined, pure-silica CIT-7 producedin fluoride media using the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium)dication is shown in FIG. 11.

The results of more expanded studies using3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium)dication are shown in Table 9A and Table 9B. In fluoride mediatedreactions CIT-7 was produced with gel compositions of Si/Al=25, 50, 100,250 and in hydroxide mediated reactions CIT-7 was produced with a gelcomposition of Si/Al=15. With H₂O/SiO₂=7, in fluoride mediatedreactions, the product was pure-silica STW (Table 9A). This phase hasalready been reported using several different imidazolium based OSDAs.When the water contents of the reactions were decreased to H₂O/SiO₂=4,the OSDA led to the formation of a previously unknown phase. The XPD ofthe calcined material is shown in FIG. 11. Under these synthesisconditions, CIT-7 was found to crystallize along with STW as a competingphase, so care had to be taken to avoid the formation of STW. Once apure-phase CIT-7 was obtained, seeds of CIT-7 were used in subsequentreactions to favor its formation over that of STW. In hydroxide mediatedreactions, at Si/Al=15 (Table 9B), without the addition of seeds, IWVwas found as the product. See FIG. 26A/B. IWV is a 2-dimensional,12-membered ring material that contains 14-membered rings that are onlyaccessible through 12-membered rings. The aluminosilicate was firstreported as ITQ-27, and was made using diphenyldimethylphosphonium asthe OSDA. The synthesis is only reported at a difficult to achievecomposition of:

1 SiO₂:0.014Al₂O₃:0.50 Me₂Ph₂POH:0.50 HF:4.2H₂O, and takes 59 days toform, the addition of seeds only shortens this by one week.

With the addition of pure-silica CIT-7 seeds to the aluminosilicatesyntheses in hydroxide media, CIT-7 was produced instead of IWV.Aluminosilicate CIT-7 could be easily obtained in hydroxide media at gelcompositions of Si/Al=5-15. Higher silica compositions led to productscontaining CIT-7 along with dense phases or ITQ-27. It is likely thatoptimizing these synthesis conditions will lead to higher silicaproducts using a hydroxide mediated synthesis, however, thesecompositions are already accessible using the fluoride method. Todemonstrate that the aluminum was in the framework, the calcined sampleswith the highest aluminum contents in both fluoride and hydroxide mediawere investigated by using ²⁷Al NMR (FIG. 24). In the sample prepared inhydroxide media, 95% of the aluminum was tetrahedral, and in the samplesynthesized in fluoride media 88% was in tetrahedral coordination. Inboth of these samples, the majority of the aluminum was in tetrahedralcoordination, demonstrating incorporation in the framework. The Si/Alrange over which CIT-7 can be produced will allow for a wide variety ofcatalytic testing to be performed.

An XRD of calcined aluminosilicate CIT-7 made with gel Si/Al=50 influoride media is shown in FIG. 12 and an XRD of the as-made materialproduced in hydroxide media with gel Si/Al=15 is shown in FIG. 13.

TABLE 9A Fluoride mediated synthesis results using 4 carbon chain linkeddiquat Gel Ratios Product Ratios^(b) Si/Al Si/Ti H₂)/SiO₂ Seeds Temp (°C.) Time (days) Result Si/Al Si/Ti ∞ — 4 None 175 8 STW^(a) — — ∞ — 4None 175 6 STW+CIT-7^(a) — — ∞ — 4 None 175 6 CIT-7^(a) — — ∞ — 4 SilicaCIT-7 175 6 CIT-7 — — ∞ — 7 None 175 6 STW — — 15 — 4 Silica CIT-7 175 5CIT-7 10 — 15 — 4 Silica CIT-7 175 5 CIT-8P 20 — 4 None 175 20 CIT-7 14— 20 — 4 None 175 12 CIT-7 13 — 25 — 4 Silica CIT-7 175 5 CIT-7 15 — 25— 4 Silica CIT-7 175 5 CIT-7 17 — 25 — 4 Silica CIT-7 175 6 CIT-7 14 —50 — 4 None 175 18 CIT-7 27 — 50 — 4 Silica CIT-7 175 4 CIT-7 28 — 100 —4 Silica CIT-7 175 4 CIT-7 36 — 250 — 4 Silica CIT-7 175 4 CIT-7 225 — —50 4 Silica CIT-7 175 7 CIT-7 — 63 — 100 4 Silica CIT-7 175 7 CIT-7 — 88^(a)Since STW and CIT-7 were competing products some syntheses producedpure phase versions (per XPD) of those molecular sieves ^(b)Determinedusing EDS of calcined material

TABLE 9B Hydroxide mediated synthesis results using 4 carbon chainlinked diquat. Gel Gel Gel Gel Temp Time Product Si/Al Na/Si ROH/SiH₂O/Si (° C.) Seeds (days) Product Si/Al  5^(a) 0.25 0.16 30 160 Silica35 CIT-7  9 CIT-7 10^(a) 0.25 0.16 30 160 None 20 CIT-7 12 15^(a) 0.160.16 30 160 None 35 IWV 15^(a) 0.16 0.16 30 160 Silica 10 CIT-7 18.4CIT-7 H⁺ form 15^(a) 0.16 0.16 30 160 Silica 10 CIT-7  9 CIT-7 30^(b)175 None 18 IWV 29 30^(b) 175 Silica 23 IWV + CIT-7 CIT-7 ^(a)Made usingLudox AS-40 and sodium aluminate ^(b)Made from CBV760

Example 8.2. Structure of CIT-7

The structure of pure silica CIT-7 was solved by 3-dimensional electrondiffraction tomography data (FIG. 14), refined by synchrotron X-raypowder diffraction data (FIG. 15). There are 10 unique/independent Tatoms in the unit cell and the material has P-1 symmetry. The newmicroporous material structure has a 2-dimensional 10-/8-ring channelsystem, with distorted 8-ring channels. The channel dimensions of thematerial are 6.2 Å*5.1 Å and 5.5 Å*2.9 Å for the 10-membered rings and8-membered rings, respectively, and views of the channel systems areshown in FIG. 16 and FIG. 17.

The structure of CIT-7 is comprised of two different secondary buildingunits. The first is the previously observed [4²5⁴6²] mtw unit. Thesecond building unit is a new [4⁴5²] building unit comprised of four4-rings and two 5-rings and are denoted here cse. This cse building unithas not been previously reported. Both building units are shown in FIG.18. The two building units then assemble to form the 3-dimensionalstructure of CIT-7, shown in FIG. 19. Oval 8-rings are created (2.9Å×5.5 Å opening, with the oxygen diameter of 2.70 Å subtracted). Thelayer that has 8-rings, could again link to itself and form 10-ringchannels (5.1 Å×6.2 Å opening, with the oxygen diameter of 2.70 Åsubtracted) that are running perpendicular to the layer and intersectedby 8-ring channels. At each intersection, a [4⁸5⁴6⁸8²10²] cavity iscreated (FIG. 19). Isosurface contours of the final material are shownin FIG. 20. One of the interesting features of the framework,highlighted in FIG. 20, are the bumps inside the 10-ring system thatcome from the 8-rings.

It should be noted that the structure of CIT-7 is not predicted in anyhypothetical zeolite framework databases as these databases only containstructures having less than 10 unique T atoms per unit cell. Theoptimized framework energy of pure-silica CIT-7 relative to α-quartz,i.e., 16.63 kJ/mol per Si atom, clearly demonstrates that this structureis energetically favorable.

Example 8.3. Pure Silicate CIT-7 Characterization

The pure silica CIT-7 produced with the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium)dication has been characterized using ¹³C CP-MAS NMR, ²⁹Si MAS NMR andArgon adsorption. The ¹³C CP-MAS NMR of the as-made material (FIG. 21)showed that the3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium)dication was occluded intact in the framework, demonstrating that it wasnot a decomposition product that formed the CIT-7. The thermogravimetricanalysis showed a weight loss of 22.5 wt %, which corresponds to 1molecule of OSDA and 2 fluoride anions per unit cell. The Argon isothermof the calcined material (FIG. 22) gave a micropore volume of 0.19cm³/g, which is consistent with the structure solution. An ¹⁹F NMRspectrum of the as-made material revealed resonances at −45 ppm and −128ppm. The resonance at −128 ppm can be assigned to a small amount of SiF₆in the sample, and the resonance at −45 ppm is consistent with fluoridebeing occluded in a pure-silica material. The ²⁹Si NMR spectrum of thecalcined material is shown in FIG. 23. The spectrum was deconvolutedusing Lorentzian lineshapes and the peak fit is shown in FIG. 24 alongwith the extracted parameters in Table 10.

TABLE 10 Deconvolution parameters determined from ²⁹Si MAS NMR Spectrumof calcined pure silica CIT-7 along with the normalized peak areas andassigned T sites Normalized Assigned Average Location Area T siteSi—O—Si Angle^(a) −115.6 0.92 Si10 152.2 −115.2 2.14 Si3 + Si8 151.7,151.6 −111.3 1.97 Si1 + Si5 149.4, 149.1 −111.0 1.06 Si6 148.3 −109.60.97 Si9 147.2 −109.3 0.88 Si4 147.2 −108.8 1.28 Si7 146.8 −106.7 1.00Si2 145.6

Example 8.5. X-Ray Analysis of CIT-7

The structure of the calcined, pure-silica material was determined usinga combination of synchrotron XPD and RED data. The calcined, pure-silicaCIT-7 powder sample was packed into a 0.5 mm glass capillary and sealed.High-resolution XPD data were then collected on the 2-1 PowderDiffraction beamline at the Stanford Synchrotron Radiation Lightsource(SSRL).

The XPD pattern could be indexed with a triclinic unit cell (a=13.020 Å,b=11.205 Å, c=9.375 Å, α=92.8°, β=107.2°, γ=103.3°), using the programTREOR (as described in P. E. Werner, et al., J. Appl. Cryst., 1985, 18,367-370) implemented in the software CMPR (as described in B. H. Toby,J. Appl. Cryst., 2005, 38, 1040-1041). No indexing solutions on highersymmetry crystal systems could be found. Individual reflectionintensities were extracted from the powder pattern to a minimumd-spacing of 0.90 Å (ca. 67.5° 20) using the program EXTRACT (describedin Baerlocher, C. EXTRACT. A Fortran program for the extraction ofintegrated intensities from a powder pattern; Institut fürKristallographie, ETH Zürich, Switzerland, 1990) in the XRS-82 suite ofprograms (see Baerlocher, C.; Hepp, A. XRS-82. X-ray Rietveld Syst.Inst. für Krist. ETH Zürich, Switzerland, 1982). Structure solutionusing these data was then attempted using both the zeolite-specificstructure-solution program Focus (R. W. Grosse-Kunstleve, et al., J.Appl. Crystallogr., 1997, 30, 985-995), and the powder charge-flippingalgorithm (C. Baerlocher, et al., Z. Kristallogr., 2007, 222, 47-53) inthe program Superflip (L. Palatinus and G. Chapuis, J. Appl. Cryst.,2007, 40, 786-790.). Unfortunately, neither approach yielded areasonable structural model.

Therefore, the RED technique was applied to the CIT-7 sample to obtain3-dimensional single-crystal data. Two independent RED data sets werecollected on two tiny crystallites, both could be indexed on triclinicunit cells that are similar to the one found for the XPD pattern.Reflection intensities (ca. 1.0 Å resolution) were then extracted foreach data set using the RED software, and were further analyzed by theprogram Triple (Triple http//www.calidris-em.com/triple.php. AccessedDec. 8, 2014). Although both datasets gave data completeness of only ca.55%, one did provide better quality over the other, i.e., the agreementfactor of the reflection intensities for Friedel pairs is 11.7% versus22.1%. Therefore, a structure solution attempt using the better REDdataset for Focus structure solution (assuming the centro-symmetricspace group P-1) was performed. Many framework topologies were proposedby Focus, but none were chemically reasonable. Luckily, the twoavailable RED datasets covered different areas of reciprocal space, andtherefore by merging them, the data completeness could be improved to86%. With the merged dataset included in the Focus runs, the structuresolution became surprisingly straightforward. A model with 10 uniqueframework T-atoms, clearly showing a 2-dimensional channel system ofintersecting 10- and 8-rings, was revealed. Indeed, this was the onlysolution proposed by the structure solution program.

The geometry of the CIT-7 framework structure model from the Focus runwas optimized using the program DLS-76 (Baerlocher, C.; Hepp, A.; Meier,W. M. DLS-76; Inst. für Krist. ETH Zürich, Switzerland, 1976), and thenserved as a starting point for Rietveld refinement, using thesynchrotron XPD data. Geometric restraints were applied on the bonddistances and bond angles of the framework atoms, and their positionsrefined. These restraints were imposed throughout the refinement, buttheir relative weighting with respect to the XPD data was reduced as therefinement progressed. The structural model finally converged withR_(F)=0.055 and R_(wp)=0.077 (R_(exp)=0.068). All atoms were refinedisotropically using scattering factors for neutral atoms. Thedisplacement parameters for similar atoms were constrained to be equalto keep the number of parameters to a minimum. Details of the refinementand selected bond distances and angles are given in Table 11. The fit ofthe profile calculated from the final model to the experimental data isshown in FIG. 15.

TABLE 11 Crystallographic data for pure-silica CIT-7. Chemicalcomposition [Si₂₀O₄₀] Unit cell a (Å) 13.0187(1) B (Å) 11.2063(1) c (Å)9.3758(1) α (°) 92.8224(6) β (°) 107.2048(5) γ (°) 103.2565 (5) Spacegroup P-1 Number of observations 8001 Number of contributing reflections3703 Number of geometric restraints 120 Number of structural parameters98 Number of profile parameters 12 R_(F) 0.041 R_(wp) 0.077 R_(exp)0.068 Selected bond distances (Å) and angles (°) Si—O (Å) min: 1.59 max:1.62 avg: 1.61 Si—O—Si (°) min: 142.1 max: 112.2 avg: 109.5 O—Si—O (°)min: 106.4 max: 157.3 avg: 148.9

Example 8.4. Titanosilicate CIT-7

The ability of the CIT-7 framework to incorporate heteroatoms besidesaluminum was tested by adding titanium to fluoride syntheses. In thetitanosilicate material, both Si/Ti=50 and 100 were synthesized. DRUV ofthe as-made and calcined titanosilicate materials was used to show thatthe titanium was present in tetrahedral coordination (FIG. 25),indicating framework incorporation.

Example 8.5. Comparison with Other Structures

The structure solution of CIT-7 shows that it is a unique frameworkcomprised of a 2-dimensional system of 10- and 8-membered rings, wherethe 8-membered rings are elliptical and the 10-membered rings contain“bumps” in them caused by the 8-membered rings. Due to this unique poresystem it is expected that this material will exhibit unique properties.

Four other zeolite frameworks, i.e., FER (e.g., NU-23, ZSM-35), MFS(e.g., ZSM-57), RRO (e.g., RUB-41) and STI (e.g., TNU-10, SSZ-75), havea 2-dimensional 10-/8-ring channel systems. CIT-7 distinguishes itselffrom these known materials by some unique structural features. CIT-7 isthe only system that has a large cavity in the intersection region. Themaximum included sphere diameter for the idealized CIT-7 framework(i.e., the one after distance-angle least-square refinement) iscalculated to be 7.91 Å, significantly larger than those for the otherfour idealized frameworks (Table 12). Also, it should also be noted thatCIT-7 can be made across a very wide Si/Al ratio (9-∞) as well as atitanium (and we suspect other heteroatoms) containing material. Thiscompositional flexibility, when combined with the medium-/small-porechannels and intersecting cavities, could be of interest in a broadspectrum of applications.

TABLE 12 Comparison of the channel and pore characteristics for the five2-D 10-/8-ring zeolites. For the 4 known zeoliteframeworks, the channelcharacteristics are taken from the literature, and the porecharacteristics are taken from the Database of Zeolite Structures. Thechannel characteristics for CIT-7 are calculated using the program“Sphere Viewer”. All data are in Å. Framework D_(M) D_(a) D_(b) D_(c)Material 10-MR opening 8-MR opening Idealized CIT-7 7.91 1.87 2.92 4.67CIT-7 5.1 × 6.2 2.9 × 5.5 MFS 6.71 5.31 3.14 1.51 ZSM-57 5.1 × 5.4 3.3 ×4.8 FER 6.25 1.50 3.34 4.63 Ferrierite 4.2 × 5.4 3.5 × 4.8 STI 6.23 4.882.90 1.79 SSZ-75 4.7 × 5.0 2.7 × 5.6 RRO 4.40 4.03 1.48 3.07 RUB-41 4.0× 6.5 2.7 × 5.0 Note: D_(M) means the maximum included sphere diameters,D_(a), D_(b) and D_(c) are the maximum free sphere diameters that candiffuse along a-, b- and c-axis, respectively.

Example 8.6. Proposed Uses of Crystalline Solids Containing 8-/10-MRs

Several systems comprising 2-dimensional systems of 10- and 8-memberedrings have been proposed for various applications such as carbonylation,NOx reduction, dewaxing, cracking, isomerization, reforming, methanol toolefins reaction, oligomerization, amination of alcohols,hydroconversion and gas separations and detailed applications andreferences for several of the frameworks are given in Table 13. CIT-7 isexpected to be useful in each of these applications, and the use of thismaterial in these applications is considered within the scope of thepresent invention. That is, various embodiments of the present inventioninclude those where the named reaction is mediated by CIT-7; i.e.,individual embodiments provide for effecting the named reaction bycontacting an appropriate feedstock with the CIT-7-type material, underconditions known to be effective for the transformation.

TABLE 13 Expected uses of microporous material frameworks with2-dimensional 10-/8-membered ring systems Framework Use As Described in:FER (NU-23, Low temperature carbonylation of DME with CO Y.Román-Leshkov, et al., J. ZSM-35) Phys. Chem. C. 115 (2011) 1096-1102.NOx reduction with methane Y. Li, et al., Appl. Catal. B Environ. 3(1993) L1-L11. Dewaxing, cracking, isomerization and reforming. U.S.Pat. No. 4,925,548. (1990) Polymerization, aromatization, cracking,hydrocracking, U.S. Pat. No. 4,016,245. (1977) converting lightaliphatics to aromatics MFS (ZSM-57) Cracking, dehydrogenating,converting paraffins to U.S. Pat. No. 4,873,067. (1989) aromatics, MTO,isomerizing xylenes, disproportionating toluene, alkylating aromatichydrocarbons, upgrading hydrocarbons 1-Butene Skeletal Isomerization andn-Octane Cracking S. Lee, et al., J. Catal. 196 (2000) 158-166 Alkeneoligomerization J.A. Martens, et al., Angew. Chemie. 39 (2000) 4376-4379RRO (RUB-41) Synthesis of methylamines by the amination of B.Tijsebaert, et al., J. Catal. methanol 278 (2011) 246-252 and B. Yilmaz,et al., Chem. Commun. (Camb). 47 (2011) 1812-4. Separation and sorptionof C3-C6 alkanes Y.X. Wang, et al., Chem. Mater. 17 (2005) 43-49 Decanehydroconversion B. Yilmaz, et al., Chem. Commun (Camb). 47 (2011)1812-4. STI (TNU-10, Skeletal isomerization of 1-butene to isobutene andthe S.B. Hong, et al., J. Am. Chem. SSZ-75) selective reduction of NOwith methane Soc. 126 (2004) 5817-26. Gas separations, convertingoxygenates (e.g. methanol) U.S. Pat. No. 7,713,512. (2010) to olefins,making small amines, NOx reduction, cold start hydrocarbon trap

Example 9.1. Synthesis of High Silica Zeolites with the HEU Topology:Introduction

New methods have been discovered to produce zeolites with the HEUframework topology with higher than previously reported silica toalumina ratios. This material, denoted herein as CIT-8, can be preparedby both direct synthesis in hydroxide media or as a topotacticcondensation product, where the layered precursor is made in fluoridemedia and denoted CIT-8P. These materials are stable to calcination andsubsequent ion exchange (if applicable) and have micropore volumeaccessible to nitrogen.

Zeolites with the HEU framework topology exist as both natural mineralsas well as synthetic analogs. The heulandite framework consists of a twodimensional channel system. In the [001] directing there are 10-memberedrings (MRs) as well as 8-MRs. Additionally, there is another set of8-MRs along with [100] direction (See Table 1).

Methods to prepare high silica heulandite, denoted CIT-8, are reportedherein. In one method, CIT-8 is prepared via topotactic condensation ofa layered aluminosilicate material containing an organic structuredirecting agent. This layered material is denoted CIT-8P. CIT-8 can alsobe prepared by direct synthesis in hydroxide media using an organicstructure directing agent (OSDA)

Example 9.2. Synthesis of High Silica Zeolites with the HEU and IWVTopologies: Results

The diquat used to prepare solids having HEU topology,3,3′-(butane-1,4-diyl)bis(1,2,4,5-tetramethyl-1H-imidazol-3-ium), isalso described above in the context of CIT-7.

However, it was found that a certain set of conditions led to theformation of a new, layered material, denoted CIT-8P. A representativepowder x-ray diffraction pattern (PXRD) of this material is shown inFIG. 27. This material was produced in low-water, fluoride-mediatedaluminosilicate reactions. The general composition of these reactionswas1SiO₂ :xAl:0.5ROH:0.5HF:4H₂Oand x was varied to give a range of Si/Al ratios. With Si/Al=15 and 20,pure phase CIT-8P was obtained. However, at Si/Al=30, 50 and 100 theproduct was a mixture of CIT-8P and CIT-7. When CIT-8P was calcined anew phase was found, a representative XRD pattern is shown in FIG. 28.This material was identified as having the HEU framework topology. Thematerial with Si/Al=20 in the gel was found to have a product Si/Al=11.5and the nitrogen adsorption isotherm gave a micropore volume of 0.096cc/g (t-plot method).

In changing the OSDA by changing the length of the linker between theimidazolium groups it was found that diquats of other linker lengthscould also form CIT-8P and CIT-8. Results of the various synthesisconditions with the diquats are shown in Table 14.

TABLE 14 Diquat synthesis results in fluoride media, 175° C.:

n = 3, 4, 5, 6, 8, 10 Linker Pure Si, Pure Si, H₂O/SiO₂ = 4, H₂O/SiO₂ =7, H₂O/SiO₂ = 4, H₂O/SiO₂ = 7, length H₂O/SiO₂ = 4 H₂O/SiO₂ = 7 Si/Al =20 Si/Al = 20 Si/Al = 50 Si/Al = 50 3 STW Amph PREFER CIT-8P + CIT-7dense PREFER 4 CIT-7, STW + Layered + CIT-8P, CIT- CIT-7 CIT-7 CIT-7CIT-7 STW 7 5 RTH, BEA CIT-8P CIT-8P CIT-7 + CIT- IWV Layered 8P STW 6BEA BEA CIP-8P BEA Unknown STF 8 BEA BEA BEA dense BEA BEA 10 BEA MTWBEA BEA BEA BEAIn general the longest diquats gave products which are commonly found inmicroporous materials syntheses such as MTW and BEA. However, thediquats with carbon chains of 3, 4, and 5 carbon atoms gave a wide rangeof interesting products. In pure silica media the 3 carbon diquat gaveSTW as a product. Under different conditions this diquat also gavePREFER, which has been previously synthesized (Schreyeck, L, et al.,Microporous Mater. 1996, 6, 259).

The four carbon diquat also led to a wide variety of products. Thisdiquat was shown to make CIT-7 in Example 8. In addition to CIT-7, thisdiquat also led to CIT-8P. Another product with this diquat is denoted“Layered+STW.” This material is likely pure silica STW plus some layeredmaterial made from the organic which disappears after calcination.

Additional experiments showed that the window for producing the HEUmaterial is narrow, at least for the tested diquat, as shown in Table15:

TABLE 15 Diquat synthesis results in fluoride media, using the diquatwith the four carbon chain linker:

for the system 1 SiO₂:x Al:0.5 ROH:0.5 HF:4 H₂O: Gel Gel Gel Gel Temp,Time Product Si/Al Na/Si ROH/Si H₂O/Si ° C. Seeds (days) Product Si/Al 5^(a) 0.25 0.16 30 160 None 43 HEU 7.3  5^(a) 0.25 0.16 30 160 Silica35 CIT-7 9 CIT-7  5^(a) 0.25 0.16 30 160 HEU 24 HEU  7.5^(a) 0.25 0.1630 160 HEU 20 CIT-7 10^(a) 0.25 0.16 30 160 HEU 20 CIT-7 10^(a) 0.250.16 30 160 HEU 20 CIT-7 12 15^(a) 0.16 0.16 30 160 None 35 CIT-7 15^(a)0.16 0.16 30 160 Silica 10 IWV 18.4 CIT-7 prot.form 15^(a) 0.16 0.16 30160 Silica 10 CIT-7 9 CIT-7 30^(b) 175 None 18 IWV 29 30^(b) 175 Silica23 IWV + CIT-7 CIT-7 ^(a) Made using Ludox AS-40 and sodium aluminate^(b) Masde from CBV760

The five carbon diquat led to a wide variety of products. In thelow-water, pure-silica case both RTH and layered STW were observed asproducts. The material called layered STW, is different than the oneformed with the four carbon diquat, but is also likely pure silica STWplus some layered material made from the organic which disappears aftercalcination. Besides CIT-7 and CIT-8P the other product formed by thefive carbon diquat was IWV. IWV is a 2-dimensional 12-membered ringmaterial that contains 14-membered rings which are only accessiblethrough 12-membered rings. This aluminosilicate was first reported asITQ-27, and was made using diphenyldimethylphosphonium as the OSDA. Thesynthesis is only reported at a difficult to achieve composition of 1SiO₂:0.014Al₂O₃:0.50 Me₂Ph₂POH:0.50 HF:4.2H₂O, and takes 59 days toform, which can only be shortened by one week using seeds.

In hydroxide media using the 4 carbon chain diquat, CIT-8 was found toform by direct synthesis at low Si/Al ratios. With a gel composition of1SiO₂:0.1Al₂O₃:0.125Na₂O:0.16R_(1/2)OH:30H₂O,HEU was found as the product after 43 days, which could be shortened to24 days by adding seeds, a representative PXRD of the calcined materialis shown in FIG. 29. This material was stable to ammonium exchange andsubsequent calcination and it was found that in proton form the materialhad a nitrogen adsorption isotherm micropore volume of 0.095 cc/g(t-plot method). The material had an organic content of 8.4 wt % and aproduct Si/Al=7.3, high than what is reported for any previous HEUsyntheses. When the Si/Al ratio was increased above about 5 in hydroxidemedia, CIT-7 was found as the product instead of HEU, even when seedswere used.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present inventioncontemplates and claims those inventions resulting from the combinationof features of the invention cited herein and those of the cited priorart references which complement the features of the present invention.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis invention.

The disclosures of each patent, patent application, and publicationcited or described in this document are hereby incorporated herein byreference, each in its entirety, for all purposes.

What is claimed:
 1. A process comprising hydrothermally treating acomposition comprising: (a) (i) at least one source of a silicon oxide,germanium oxide, or combination thereof; and optionally (ii) at leastone source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide,iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide,zirconium oxide, or combination or mixture thereof; and (b) a linkedpair of quaternary imidazolium cations of a structure:

under conditions effective to crystallize a crystalline microporoussolid of IWV topology; wherein t is 3, 4, 5, or 6; and R isindependently methyl or ethyl, and n is independently 1, 2, or 3; saidlinked pair of quaternary imidazolium cations having associated fluorideor hydroxide ions.
 2. The process of claim 1, wherein the linked pair ofquaternary imidazolium cations has a structure:

and t is 4, 5, or 6, said linked pair of quaternary imidazolium cationshaving associated hydroxide ions.
 3. The process of claim 1, wherein thecomposition comprises at least one source of a silicon oxide and atleast one source of aluminum oxide.
 4. The process of claim 1, thecomposition further comprising aqueous HF.
 5. The process of claim 1,the composition further comprising aqueous hydroxide.
 6. The process ofclaim 1, wherein the hydrothermally treating is done at a temperature ina range of from about 100° C. to about 200° C. for a time effective forcrystallizing the crystalline microporous solid of IWV topology.
 7. Theprocess of claim 1, further comprising isolating the crystallinemicroporous solid of IWV topology.
 8. The process of claim 7, furthercomprising calcining the isolated crystalline microporous solid of IWVtopology at a temperature in a range of from about 350° C. to about 850°C. to form a calcined crystalline microporous solid of IWV topology. 9.The process of claim 8, further comprising treating the calcinedcrystalline microporous solid of IWV topology with an aqueous ammoniumsalt.
 10. The process of claim 7, further comprising treating the poresof the calcined crystalline microporous solid of IWV topology with atleast one type of transition metal or transition metal oxide.
 11. Acomposition used in the process of claim 1, the composition comprising:(a) (i) the at least one source of a silicon oxide, germanium oxide, orcombination thereof; and optionally (ii) the at least one source ofaluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconiumoxide, or combination or mixture thereof; and (b) the linked pair ofquaternary imidazolium cations of a structure:

wherein t is 3, 4, 5, or 6; and R is independently methyl or ethyl, andn is independently 1, 2, or 3; and (c) a compositionally consistentcrystalline microporous solid of IWV topology; said linked pair ofquaternary imidazolium cations having associated fluoride or hydroxideions.
 12. The composition of claim 11, containing the at least onesource of silicon oxide, the linked pair of quaternary imidazoliumcations, and the compositionally consistent crystalline microporoussolid of IWV topology.
 13. The composition of claim 11, wherein aportion of the crystalline microporous solid of IWV topology containsthe linked pair of quaternary imidazolium cations.
 14. The compositionof claim 11, wherein the composition further comprises aqueous HF. 15.The composition of claim 11, wherein the composition further comprisesaqueous hydroxide.
 16. The composition of claim 14 or 15 that is a gel.17. A crystalline microporous solid of IWV topology prepared by theprocess of claim 1, the crystalline microporous solid of IWV topologyhaving pores, at least some of which are occluded with linked pairs ofquaternary imidazolium cations having a structure:

wherein t is 3, 4, 5, or 6; and R is independently methyl or ethyl, andn is independently 1, 2, or
 3. 18. A crystalline microporousaluminosilicate solid of IWV topology prepared by the process of claim3, the crystalline microporous solid of IWV topology having pores atleast some of which are occluded with linked pairs of quaternaryimidazolium cations having a structure:

wherein t is 3, 4, 5, or 6; R is independently methyl or ethyl, and n isindependently 1, 2, or
 3. 19. The crystalline microporous solid of IWVtopology of claim 18, wherein the linked pair of quaternary imidazoliumcations has a structure:

and t is 4, 5, or 6, said linked pair of quaternary imidazolium cationshaving associated hydroxide ions.
 20. The crystalline microporous solidof IWV topology of claim 18, the aluminosilicate having an Si:Al ratioin a range of from about 5:1 to about 250:1.
 21. The crystallinemicroporous solid of IWV topology of claim 17 that exhibits an XRDdiffraction pattern the same as or consistent with those shown in FIG.26A or FIG. 26B.
 22. The crystalline microporous solid of IWV topologyof claim 17 that exhibits an XRD pattern having at least of the fivemajor peaks selected from 6.02±0.15° 2-theta; 6.40±0.15° 2-theta;7.09±0.15° 2-theta; 7.90±0.15° 2-theta; 7.99±0.15° 2-theta; 9.49±0.15°2-theta; 12.85±0.15° 2-theta; 19.04±0.15° 2-theta; 21.07±0.15° 2-theta;and 26.71±0.15° 2-theta.
 23. The crystalline microporous solid of IWVtopology of claim 17, the framework comprising silicon oxide.
 24. Thecrystalline microporous solid of IWV topology of claim 17, wherein thelinked pair of quaternary imidazolium cations has a structure:

and t is 4, 5, or 6, said linked pair of quaternary imidazolium cationshaving associated hydroxide ions.